Acetylene derivatives and crop protection agents containing them

ABSTRACT

Acetylene derivatives of the general formula I ##STR1## where U, V and W are hydrogen, halogen, nitro, cyano, alkyl or alkoxy, 
     A is alkylidene, alkoxymethylidene, alkylthiomethylidene or alkoximino, 
     B is OH, alkoxy or alkylamino and 
     R is hydrogen, halogen, cyano, CF 3 , alkyl, cycloalkyl, haloalkyl, aryl, alkenyl, alkynyl, heterocyclyl, hetaryl, arylalkyl, arylalkenyl, arylethynyl, hetaryl-C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy-C 1  -C 4  -alkyl, aryloxyalkyl, hetaryloxyalkyl, arylamino-alkyl, arylthiomethyl, hetarylthiomethyl, C(O)R 1 , C(O)NR 2  R 3 , C(S)NR 4  R 5 , C(O)SR 6 , C(S)OR 7 , C(S)SR 8 , CH(OH)R 9 , CH(OR 10 )R 11 , SiR 12  R 13  R 14 , SnR 15  R 16  R 17 , C(OR)R 18  or C(═N--OR 19 )R 20  and 
     R 1  -R 17 , R 19  and R 20  are hydrogen, alkyl, aryl, hetaryl, arylalkyl or hetarylalkyl and R 18  is OH, C 1  -C 4  -alkoxy or aryl-C 1  -C 4  -alkoxy, and fungicides containing these compounds.

The present invention relates to novel acetylene derivatives and amethod for controlling pests, in particular fungi, insects, nematodesand spider mites, with these compounds.

It is known that individual acetylene derivatives (European Patents178,826, 244,077, 253,213, 280,185 and 477,631) have fungicidal orinsecticidal activity. However, their activity is unsatisfactory.

We have found, surprisingly, that the novel acetylene derivatives of thegeneral formula I ##STR2## where

U, V and W are identical or different and are each hydrogen, halogen,nitro, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,

A is C₁ -C₄ -alkylidene, C₁ -C₄ -alkoxymethylidene, C₁ -C₄-alkylthiomethylidene or C₁ -C₄ -alkoximino,

B is OH, C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino, and

R is hydrogen, halogen, cyano, CF₃, straight-chain or branched C₁ -C₁₀-alkyl, C₃ -C₆ -cycloalkyl, unsubstituted or substituted aryl, halo-C₁-C₄ -alkyl, C₂ -C₆ -alkenyl, C₂ -C₄ -alkynyl, unsubstituted orsubstituted heterocyclyl, unsubstituted or substituted hetaryl,unsubstituted or substituted aryl-C₁ -C₄ -alkyl, unsubstituted orsubstituted aryl-C₂ -C₄ -alkenyl, unsubstituted or substitutedarylethynyl, unsubstituted or substituted hetaryl-C₁ -C₄ -alkyl, C₁ -C₄-alkoxy-C₁ -C₄ -alkyl, unsubstituted or substituted aryloxy-C₁ -C₄-alkyl, unsubstituted or substituted hetaryloxy-C₁ -C₄ -alkyl,unsubstituted or substituted arylamino-C₁ -C₄ -alkyl, unsubstituted orsubstituted arylthiomethyl, unsubstituted or substitutedhetarylthiomethyl, C(O)R¹, C(O)NR² R³, C(S)NR⁴ R⁵, C(O)SR⁶, C(S)OR⁷,C(S)SR⁸, CH(OH)R⁹, CH(OR¹⁰)R¹¹, SiR¹² R¹³ R¹⁴, SnR¹⁵ R¹⁶ R¹⁷, C(O)R¹⁸ orC(═N--OR¹⁹)R²⁰ and

R¹ -R¹⁷, R¹⁹ and R²⁰ are identical or different and are each hydrogen,C₁ -C₄ -alkyl, unsubstituted or substituted aryl, unsubstituted orsubstituted hetaryl, unsubstituted or substituted arylalkyl orunsubstituted or substituted hetarylalkyl,

R¹⁸ is OH, C₁ -C₄ -alkoxy or unsubstituted or substituted aryl-C₁ -C₄-alkoxy, the term "unsubstituted or substituted" denoting, in additionto hydrogen, the substitutents halogen, cyano, nitro, C₁ -C₄ -alkyl, C₁-C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, C₁ -C₄-alkoximino-C₁ -C₄ -alkyl, aryl, aryloxy, benzyl, benzyloxy, hetaryl,hetaryloxy, C₃ -C₆ -cycloalkyl, C₁ -C₄ -dialkylamino, CO₂ Me, CO₂ Et,formyl and acyl, Me being methyl, Et being ethyl and the expressionhetaryl being an aromatic five-membered or sixmembered heterocyclicstructure, with the exception of the following individual compounds ofthe general formula I where

A is CHOCH₃, B is OCH₃ and R is phenyl,

A is CHSCH₃, B is OCH₃ and R is phenyl,

A is CHCH₃, B is OCH₃ and R is phenyl, 2-fluorophenyl, 2-chlorophenyl,2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl,4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl,

A is NOCH₃, B is OCH₃ and R is phenyl, 2-fluorophenyl, 2-chlorophenyl,2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl,4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl,

A is NOCH₃, B is NHCH₃ or R is CH₃ or phenyl,

A is CHOCH₃, B is NHCH₃ and R is CH₃ or phenyl and

A is CHSCH₃, B is NHCH₃ and R is phenyl, have excellent fungicidal,insecticidal, nematicidal and acaricidal activity.

The fungicidal and insecticidal activity is preferred.

The radicals stated for the general formula I may have, for example, thefollowing meanings:

U, V and W may each be hydrogen, halogen (e.g. fluorine, chlorine,bromine or iodine), methyl or methoxy,

A may be C₁ -C₄ -alkylidene (e.g. methylidene, ethylidene,n-propylidene, isopropylidene, n-butylidene, isobutylidene,sec-butylidene or tert-butylidene), C₁ -C₄ -alkoxymethylidene t(e.g.methoxy-, ethoxy-, n-propoxy-, iso-propoxy-, n-butoxy-, isobutoxy-,sec-butoxy- or tert-butoxymethylidene), C₁ -C₄ -alkylthiomethylidene(e.g. methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, iso-butyl-,sec-butyl- or tert-butylthiomethylidene), C₁ -C₄ -alkoximino (e.g.methoximino, ethoximino, n-propoximino, isopropoximino, n-butoximino,isobutoximino, sec-butoximino or tert-butoximino),

B may be OH, C₁ -C₄ -alkoxy (e.g. methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy) or C₁ -C₄-alkylamine (e.g. methylamine, ethylamine, n-propylamine,isopropylamine, n-butylamine, isobutylamine, sec-butylamine ortert-butylamine), and

R is hydrogen, halogen (fluorine, chlorine, bromine or iodine), cyano,CF₃ straight-chain or branched C₁ -C₁₀ -alkyl (e.g. methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl or n-decyl), C₃-C₆ -cycloalkyl (e.g. cyclopropyl, cyclobutyl, cyclopentyl orcyclohexyl), unsubstituted or substituted aryl (e.g. phenyl, naphthyl oranthryl), halo-C₁ -C₄ -alkyl (e.g. bromomethyl, chloromethyl, iodomethylor CF₃ -methyl), C₂ -C₆ -alkenyl (e.g. vinyl, 1-propenyl, 2-propenyl,2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 3-methyl-2-butenyl or2-methyl-2-penten-5-yl), C₂ -C₄ -alkynyl (e.g. ethynyl or 1-propynyl),unsubstituted or substituted heterocyclyl (e.g. oxiranyl, 1-aziridinyl,1-azetidinyl, 1-pyrrolidinyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl,3-tetrahydropyranyl, 1-piperidinyl, 1-morpholinyl, 1-piperazinyl,1,3-dioxanyl, 3-tetrahydrothiopyranyl), unsubstituted or substitutedhetaryl (e.g. pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidinyl,4-pyrimidinyl, 2-pyrimidinyl, thienyl, 2-thienyl, 3-thienyl, furyl,2-furyl, 3-furyl, 1-pyrrolyl, 5-isoxazolyl, 3-isoxazolyl,1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-thiadiazol-2-yl,1-imidazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, 4-thiazolyl,2-benzothiazolyl), unsubstituted or substituted aryl-C₂ -C₄ -alkyl (e.g.benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl,3-phenylpropyl, 2-methyl-3-phenylpropyl, 2-methyl-2-phenylpropyl or4-phenylbutyl), unsubstituted or substituted aryl-C₁ -C₄ -alkenyl (e.g.phenyl-1-ethenyl, 2-phenyl-1-propenyl, 2,2-diphenylethenyl,1-phenyl-1-propen-2-yl or 1-phenyl-1-ethenyl), unsubstituted orsubstituted arylethynyl (e.g. phenylethynyl), unsubstituted orsubstituted hetaryl-C₁ -C₄ -alkyl (e.g. pyridylmethyl or3-pyridylmethyl), C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl (e.g. methoxymethyl,ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl,isobutoxymethyl, sec-butoxymethyl, tert-butoxymethyl,2-methoxyprop-2-yl, 2-ethoxyprop-2-yl, 2-n-propoxyprop-2-yl,isopropoxyprop-2-yl, 2-n-butoxyprop-2-yl, isobutoxyprop-2-yl,sec-butoxyprop-2-yl or tert-butoxyprop-2-yl), unsubstituted orsubstituted aryloxy-C₁ -C₄ -alkyl (e.g. phenoxymethyl), unsubstituted orsubstituted hetaryloxy-C₁ -C₄ -alkyl (e.g. 2-thienyloxymethyl),unsubstituted or substituted arylamino-C₁ -C₄ -alkyl (e.g.N-(phenylamino)-methyl), C(O)R¹ (e.g. C(O)CH₃, C(O)CH₂ CH₃ orC(O)phenyl), C(O)NR² R³ (e.g. C(O)NH₂, C(O)NHCH₃), C(S)NR² R³ (e.g.C(S)NH₂ or C(S)NHCH₃), C(O)SR⁶ (e.g. C(O)SCH₃ or C(O)SCH₂ C₆ H₅),C(O)OR⁷ (e.g. CO₂ CH₃ or CO₂ CH₂ C₆ H₅), C(S)SR⁸ (e.g. CS₂ CH₃),CH(OH)R⁹ (e.g. H(OH)C₆ H₅), CH(OR¹⁰)R¹¹ (e.g. CH(OCH₃)C₆ H₅), SiR¹² R¹³R¹⁴ (e.g. SiMe₃ ) SnR¹⁵ R¹⁶ R¹⁷ (e.g. SnMe₃), C(O)R¹⁸ (e.g. CO₂ Me, CO₂CH₂ C₆ H₅) or C(═N--OR¹⁹)R²⁰ (e.g. C(NOMe)C₆ H₅).

R¹ -R¹⁷, R¹⁹ and R²⁰ are, for example, hydrogen C₁ -C₄ -alkyl (e.g.methyl, ethyl, n- and isopropyl, n-, iso-, sec- and tert-butyl),unsubstituted or substituted aryl (e.g. 2-chlorophenyl,3,5-dimethylphenyl and 1-methyl-2-naphthyl), unsubstituted orsubstituted hetaryl (e.g. 6-chloro-2-pyrridyl, 4-pyrimidinyl, 2-furyland 6-methyl-benzthiazol-2-yl), unsubstituted or substituted arylalkyl(e.g. 2-chlorobenzyl and 3,5-dichlorobenzyl) and unsubstituted orsubstituted hetarylalkyl (e.g. 2-furylmethyl and6-methyl-2-pyridylmethyl) and R¹⁸ is, for example, OH, C₁ -C₄ -alkoxy(e.g. methoxy and ethoxy) and unsubstituted or substituted aryl-C₁ -C₄-alkoxy (e.g. 2-chlorobenzyloxy).

The radicals defined above as unsubstituted or substituted contain assubstituents, apart from hydrogen, for example fluorine, chlorine,bromine, iodine, cyano, nitro, methyl, ethyl, isopropyl, tert-butyl,methoxy, ethoxy, isopropoxy, tert-butoxy, trifluoromethyl, chloromethyl,dichloromethyl, trichloromethyl, trifluoromethoxy,1,1,2,2-tetrafluoroethoxy, methoximinomethyl, ethoximinomethyl,n-propoximinomethyl, n-butoximinomethyl, n-pentoximinomethyl,n-hexyloximinomethyl, allyloximinomethyl, benzyloximinomethyl,isopropoximinomethyl, isobutoximinomethyl, tert-butoximinomethyl,methylimino-1-ethyl, ethoximino-1-ethyl, n-propoximino-1-ethyl,n-butoximino-1-ethyl, n-pentoximino-1-ethyl, n-hexoximino-1-ethyl,allyloximino-1-ethyl, benzyloximino-1-ethyl, phenyl, phenoxy, benzyl,benzyloxy, imidazol-1-yl, piperazin-1-yl, 4-morpholinyl, piperidin-1-yl,pyridyl-2-oxy, cyclopropyl, cyclohexyl, oxiranyl, 1,3-dioxan-2-yl,1,3-dioxan-2-yl, tetrahydropyran-2-yloxy, dimethylamino, diethylamino,CO₂ Me, CO₂ Et, formyl or acyl, Me being methyl and Et being ethyl.

The compounds of the general formula I ##STR3## where U, V and W areeach hydrogen,

A is ethylidene, methoxymethylidene or methoximino,

B is methoxy or methylamine and

R has the abovementioned meanings, are preferred.

Owing to the C═C or C═N double bonds, the novel compounds of the generalformula I may be obtained in the preparation as E/Z isomer mixtures.These can be separated into the individual components in a conventionalmanner, for example by crystallization or chromatography. Both theindividual isomeric compounds and mixtures thereof form subjects of theinvention and can be used as pesticides.

The compounds of the general formula I as claimed in claim 1 areprepared, for example, as described in the following schemes:

The novel compounds of the general formula I can be prepared byreacting, for example, an o-bromo compound 2 with a terminal acetylenederivative 3 in the presence of a transition metal catalyst, preferablya palladium compound, e.g. Pd(PPh₃)₄, PdCl₂ or Pd(OAc)₂, in the presenceof triphenylphosphine and in the presence of a base, for example anN-alkylamine, such as triethylamine, and in the presence or absence of asolvent or diluent, e.g. dimethylformamide or acetonitrile (cf. forexample L. Brandsma et al., Synth. Comm. 20 (1990), 1889 and W. B.Austin et al., J. Org. Chem. 46 (1981), 2280). ##STR4##

A, B, R, U, V and W have the meanings stated in claim 1.

Alternatively, the compounds of the general formula 1 are obtained byreacting the o-bromo-α-keto acid derivatives 4 with the acetylenes ofthe formula 3 (conditions similar to Scheme 1) ##STR5## and thenreacting the resulting α-ketocarboxylic acid derivatives 5 a) forexample in a Wittig or a Wittig-Horner-Emmons reaction with aphosphonium ylide 6 or with a phosphonic acid derivative 7 (Scheme 3) togive the novel compounds of the formula 1, where B, U, V, W and R havethe meanings stated in claim 1 and A is CH-alkyl, CH-alkoxy orCH-thioalkyl (cf. for example C. Ferri, Reaktionen der organischenSynthese, Thieme Verlag, Stuttgart, page 354 et seq., 1978), or R'=CH₃,M.sup.⊕ =alkali metal ion Scheme 3

b) with an O-alkylhydroxylamine 8, in the presence or absence of anacid, e.g. hydrochloric acid, or of a ##STR6## bse, e.g. K₂ CO₃, to givethe novel compounds of the formula 1 in which B, U, V, W, R and R⁴ havethe meanings stated in claim 1 (cf. for example European Patent253,213). ##STR7##

The novel compounds of the general formula 1 can also be prepared byreacting the terminal acetylenes 9, by a transition metal (TM)-catalyzedcoupling, with the halides 10, preferably with the bromides (X=Br), orthe iodides (X=I) in the presence of a catalyst, e.g. PdCl₂, Pd(OAc)₂ orPd(PPh₃)₄, and of a base, such as triethylamine (cf. for example P. C.Vollhardt, Angew. Chem. 98 (1986), 268 and H. Yamanaka, Synthesis(1983), 312). Scheme 5

A, B, R, U, V and W have the meanings stated in claim 1.

In an alternative procedure, the α-keto acid derivatives of the terminalacetylenes 11 can be converted with the halides 10 under transitionmetal ##STR8## (TM)-catalysis into the derivatives 5, and the latter canbe converted as described above into the novel compounds of theformula 1. ##STR9##

In a further possible method for the preparation of the compounds of thegeneral formula 1, the acetylene group in formula 12 is first producedby a known method (cf. for example Houben-Weyl, Vol. V/2a, page 33 etseq. (Viehe) or see Schemes 1+2) ##STR10## and the group Y is thenconverted into the group ##STR11##

Schemes 7-9 are intended to illustrate this. The ketocarboxylic esters17 can be prepared starting from the o-bromobenzaldehydes 13. ##STR12##

The o-bromobenzaldehydes 12 can be reacted with the terminal acetylenes3 under transition metal catalysis to give the aldehydes 14 (cf. W. B.Austin, J. Org. Chem. 46 (1981), 2280).

The cyanohydrins 15 are obtained from the aldehydes 14 by reaction witha metal cyanide, such as NaCN or KCN, in the presence of an acid, e.g.hydrochloric acid (cf. for example Organikum, 16th Edition, page 445(1986)).

The mandelic acid derivatives 16 can be prepared from the cyanohydrins15 via a Pinner reaction (cf., for example, Org. Synth. Coll. 4 (1963),58).

Oxidation of the mandelic acid derivatives 16, for example with achromium compound, such as chromium trioxide, with sodium hypochloriteor with TEMPO gives the α-ketoesters 17 (cf. for example Houben-Weyl,Vol. 4/lb, pages 425-464 (1975); TEMPO=tetramethylpiperidin-1-oxyl).

The novel compounds of the formula 1a, in which A, U, V, W and R havethe meanings stated in claim 1 and B is CO₂ Me, can be prepared from theketoesters 17, as shown in Schemes 3 and 4. The α-ketocarboxylic esters17 can be synthesized starting from the halogen derivatives 18, byGrignard reaction with oxalic acid compounds 19 similarly to Scheme 8(cf., for example, J. S. Nimitz, J. Org. Chem. 46 (1981), 211).##STR13##

In a further possible method, carboxylic acids 20 are converted via thestage of the acyl chlorides into the cyanides 21 and the latter areconverted into the ketoesters 17 by a Pinner reaction. ##STR14## (cf.for example Organikum, 16th Edition, 423 et seq. (1986) and Angew. Chem.94 (1982), 1).

The novel compounds of the formula 1 where A, X, Y, Z and R have themeanings stated in claim 1 and B is hydroxyl or alkylamino can beprepared from the carboxylic ester derivatives 1a. ##STR15##

The carboxylic acids 22 are obtained by hydrolysis by known methods (cf.Organikum, 16th Edition, page 415 et seq. and page 622 (1986)).

They can be converted into the acyl chlorides 23 (cf. Organikum, 16thEdition, page 423 et seq. (1986)).

The amides 24 are either obtained from these in a conventional manner(Organikum, 16th Edition, page 412 (1986)) or alternatively from thecarboxylic esters 1a directly by aminolysis with amines.

However, the novel compounds of the general formula I can also beprepared by converting a suitably substituted styryl compound 25 in aconventional manner into the corresponding acetylene derivative 1.##STR16##

Where X is H and Y is halogen or X is halogen and Y is H, the reactionis carried out in the presence of a base, e.g. sodium hydride, potassiumhydroxide, Triton B or n-butyllithium (cf. for example H. Zimmer et al.,Chimia 28 (1974), page 656 et seq.) (Triton B=2-benzyltrimethylammoniumhydroxide).

Where X and Y are each halogen, the cleavage can be carried out withzinc (cf. for example H. G. Viehe, Chemistry of Acetylenes, MarcelDekker, New York, 1969, page 134 et seq.).

The Examples which follow illustrate the preparation of the compounds.

EXAMPLES Example 1

Preparation of methyl 2-ethynylphenylglyoxylate O-methyloxime (compound1, Table 2)

33.3 g (0.35 mol) of trimethylsilylacetylene, 3.8 g of palladium(II)acetate, 3.2 g of copper(I) iodide and 8.9 g of triphenylphosphine areadded to a solution of 55.4 g (0.23 mol) of methyl2-bromophenylglyoxylate in 415 ml of triethylamine, and nitrogen is thenpassed through the solution for 30 minutes. The reaction mixture is thenheated at 90° C. for 45 minutes, is allowed to cool and is filtered off.The filtrate is evaporated down, the residue is taken up in ethylacetate and the solution is washed with water. The organic phase isdried and evaporated down. 56.8 g of α-ketoester remain as a black oil.

The crude product prepared in this manner is dissolved in 50 ml ofmethanol, 38.9 g (0.37 mol) of O-methylhydroxylamine hydrochloride areadded and heating is carried out for 15 minutes at 60° C. The mixture isevaporated down, the residue is taken up in ethyl acetate and thesolution is washed with water. The organic phase is dried and evaporateddown. 52.4 g of compound No. 2 (Table 2) remain as a black oil. ¹ H-NMR(CDCl₃ /TMS): δ=0.22 (s, 9H, SiMe₃); 3.86; 4.06 (s, 3H, OCH₃); 7.25-7.61ppm (m, 4H, aryl).

The trimethylsilylacetylene compound prepared in this manner isdissolved in 320 ml of methanol and stirred together with 3.2 g ofpotassium carbonate for 1 hour at room temperature (20° C.). The mixtureis then evaporated down, the residue is taken up in methylene chlorideand the solution is washed with 10% strength sodium bicarbonatesolution. The organic phase is dried and evaporated down. 36 g (72%,based on methyl 2-bromophenylglyoxylate) of compound 1 (Table 2) remainas a black solid. ¹ H-NMR (CDCl₃ /TMS): δ=3.17 (s, 3H, ═C--H); 3.87;4.07 (s, 3H, OCH₃); 7.27-7.60 ppm (m, 4H, aryl).

Example 2

a) Preparation of methyl 2-(2-methylphenyl)-ethynylphenylglyoxylateO-methyloxime (European Patent 253,213, No. 136)

300 mg of palladium(II) acetate, 1.5 g of triphenylphosphine and 100 mgof copper(I) iodide and 11 g (0.095 mol) of 2-methylphenylacetylene areadded to a solution of 10 g (0.041 mol) of methyl2-bromophenylglyoxylate in 50 ml of triethylamine. Nitrogen is passedthrough the solution for 30 minutes, after which the solution is heatedfor 3 hours at 80° C. After cooling, methylene chloride is added and thesolution is washed with water. The organic phase is dried and evaporateddown. 16.5 g of methyl 2-(2-methylphenyl)-ethynylphenylglyoxylate remainas a black oil. ¹ H-NMR (CDCl₃ /TMS): δ=2.53 (s, 3H, CH₃); 3.81 (s, 3H,OCH₃); 7.13-7.88 ppm (m, 8H, aryl).

7.4 g (0.089 mol) of methoxyamine hydrochloride are added to theketoester obtained in this manner, in 20 ml of methanol, and refluxingis carried out for 1.5 hours. The mixture is evaporated down, theresidue is taken up in ethyl acetate, the solution is washed with waterand the organic phase is dried and evaporated down. 9.5 g of the productremain as a black oil, which can be recrystallized from methanol. Theabovementioned compound is obtained in this manner as a colorless solidhaving a melting point of 92°-96° C. ¹ H-NMR (CDCl₃ /TMS): δ=2.46 (s,3H, CH₃); 3.83; 4.07 (s, 3H, OCH₃); 7.12-7.63 ppm (m, 8H, aryl).

b) N-Methyl-2-(2-methylphenylethynyl)-phenylglyoxylamide O-methyloxime(compound 32, Table 4)

2 g (7 mmol) of the compound prepared in Example 2a are added to 50 mlof a 40% strength methylamine solution and the mixture is stirredovernight at room temperature. Extraction with ether, drying andevaporation are then carried out. 0.9 g (42%) of compound 32 (Table 4)remains as a pale yellow solid of melting point 128°-129° C. ¹ H-NMR(CDCl₃ /TMS): δ=2.43 (s, 3H, CH₃); 2.91 (d, 3H, NCH₃); 3.96 (s, 3H,OCH₃); 6.75 (br, 1H, NH); 7.14-7.63 ppm (m, 8H, aryl).

Example 3

Methyl 2-(2-(3-chloro)thienylethynyl)-phenylglyoxylate O-methyloxime(compound 178, Table 2)

100 mg of palladium(II) acetate, 87 mg of copper(I) iodide and 240 mg oftriphenylphosphine are added to a solution of 2 g (0.009 mol) of methyl2-ethynylphenylglyoxylate O-methyl oxime (Example 1) and 3.6 g (0.018mol) of 2-bromo-3-chlorothiophene in 100 ml of triethylamine. Nitrogenis passed through the solution for 30 minutes, after which the solutionis heated for 1 hour at 90° C. The solid formed is filtered off and thefiltrate is evaporated down. The residue is taken up in ethyl acetate,the solution is washed with water and the organic phase is dried andevaporated down.

The remaining crude product is chromatographed over silica gel usinghexane/methyl tert-butyl ether.

As the first fraction, 700 mg (23%) of compound 178 (Table 2) areobtained in the form of a brown oil. ¹ H-NMR (CDCl₃ /TMS): δ=3.88; 4.09(s, 3H, OCH₃); 6.93 (d, 1H, ═CH); 7.25 (d, 1H, ═CH); 7.27-7.66 ppm (m,4H, aryl).

500 mg (13%) of dimeric starting material are obtained as the secondfraction (compound 162, Table 2). ¹ H-NMR (CDCl₃ /TMS): δ=3.91; 4.09 (s,3H, OCH₃); 7.27-7.61 ppm (m, 4H, aryl).

2. Method 1: Methyl α-[2-(phenylethynyl)-phenyl]-β-methylacrylate[European Patent 280,185, No. 136]

300 mg of palladium(II) acetate, 1.5 g of triphenylphosphine and 100 mgof copper(I) iodide are added to a solution of 10 g (0.041 mol) ofmethyl 2-bromophenylglyoxylate and 6.3 g (0.061 mol) of phenylacetylenein 50 ml of triethylamine. Nitrogen is passed through the solution for30 minutes, after which the solution is heated for 90 minutes at 90° C.It is then evaporated down and the residue is taken up in methylenechloride. The solution is washed with water, dried and evaporated down.The remaining residue is chromatographed over silica gel usinghexane/methyl tert-butyl ether. 5.5 g of α-ketoester remain as a brownoil after evaporating down. ¹ H-NMR (CDCl₃ /TMS): δ=2.82 (s, 3H, CH₃);7.36-7.88 ppm (m, 9H, aryl).

2.4 g (0.021 mol) of potassium tert-butylate are added at 5° C. to asolution of 8.7 g (0.021 mol) of ethyltriphenylphosphonium iodide in 60ml of dry tetrahydrofuran. Stirring is carried out for 1 hour at thistemperature, after which a solution of 5.5 g (0.021 mol) of α-ketoester(see above) in 20 ml of tetrahydrofuran is added dropwise at 5° C. andstirring is continued for 3 hours at room temperature. The reactionbatch is poured onto water and extracted with methylene chloride, andthe organic phase is dried and evaporated down. Chromatography oversilica gel using hexane/methyl tert-butyl ether gives 1.2 g of thecompound [European Patent 280,185, No. 136] as a brown oil in the formof an E/Z mixture. ¹ H-NMR (CDCl₃ /TMS): δ=1.74 (d, 3H, CH₃ -isomer A);2.22 (d, 3H, CH₃ -isomer B); 3.70; 3.71 (s, 3H, CH₃ -isomer A, B); 6.38(q, 1H, CH); 7.17-7.61 ppm (m, 9H, aryl).

Example 4

Preparation of methylα-{2-[2-(4-chlorophenyl)-isoxazol-5-ylethynyl]-phenyl}-β-methoxyacrylate(compound 195, Table 1)

0.8 g of methylα-{2-[2-chloro-2-(3-[4-chlorophenyl]-isoxazol-5-yl)-ethenyl]-phenyl}-β-methoxyacrylate(European Patent 378,755) is dissolved in 10 ml of anhydrous dimethylsulfoxide, and a pinch of sodium hydride is added. Stirring is carriedout overnight at room temperature, and the mixture is poured onto icewater and extracted three times with dichloromethane. The combinedorganic phases are washed three times with water, dried over sodiumsulfate and then evaporated down in a rotary evaporator. The residue istriturated with diisopropyl ether. 0.3 g of the title compound isobtained as colorless crystals of melting point 107°-110° C. ¹ H-NMR(CDCl₃ /TMS), δ=3.7 (s, 3H); 3.85 (s, 3H); 6.7 (s, 1H); 7.2-7.8 (m, 9H).

Example 5

Preparation of 2-ethynylphenylglyoxylic acid-N-methylamide-O-methyloxime

1 g (4.6 mmol) of the acetylene compound prepared in Example 1 is addedto 20 ml of a 40% strength methylamine solution, and the mixture isstirred for 45 minutes at 40°-50° C. The solution is extracted withmethyl tert-butyl ether, dried and evaporated down. 700 mg (70%) of thecompound remain as a colorless solid.

¹ H-NMR (CDCl₃ /TMS): δ=2.99 (d, 2H, NCH₃); 3.13 (s, 1H, .tbd.C--H),3.98 (s, 3H, OCH₃), 6.80 (br, 1H, NH); 7.21-7.58 ppm (m, 4H).

Example 6

Preparation of methyl 2-benzoyl-ethynylphenylglyoxylate O-methyloxime(compound 26, Table 6)

Under a nitrogen blanket and at 90° C., 2 g (9.2 mmol) of the acetylenederivative from Example 1 is added to a mixture of 50 mg of copper(II)chloride, 110 mg of palladium(II) acetate, 380 mg of triphenylphosphineand 2.6 g (18.4 mmol) of benzoyl chloride in 100 ml of triethylamine.After 30 minutes, the mixture is allowed to cool and the solid isfiltered off. The filtrate is evaporaed down, and the residue is takenup in methyl tert-butyl ether, washed with water, dried and evaporateddown. The residue is stirred with diethyl ether and the precipitatedpale brown solid is filtered off. 2.0 g (68%) of compound 26, Table 6,remain. Mp. 89°-94° C.

Example 7

Preparation of methyl 2-(methoxyiminobenzoyl)ethynylphenylglyoxylateO-methyloxime (compound 10, Table 9).

A mixture of 1.5 g (4.7 mmol) of compound 26 from Table 6 (from Example6) and 2.6 g of O-methylhydroxylamine hydrochloride in 5 ml of methanolis heated for 90 min at 60° C. The mixture is evaporated down and theresidue is taken up in methyl tert-butyl ether and washed with water,followed by drying and evaporating down. The residue is chromatographedon silica gel using mixtures of methyl tert-butyl ether and hexane. 1.1g (67%) of compound 10 from Table 9 remain as a yellow oil (isomermixture).

¹ H-NMR (CDCl₃ /TMS): δ=3.81; 4.04; 4.12 (3H, OCH₃); 7.28-7.88 ppm (9H).

                  TABLE 1                                                         ______________________________________                                         ##STR17##                                                                                                phys. data                                                                    (m.p. [°C.]);                                                          IR [cm.sup.-1 ];                                  No.  R                      .sup.1 H-NMR [δ scale]                      ______________________________________                                         1   H                                                                         2   SiMe.sub.3                                                                3   S.sub.n Me.sub.3                                                          4   I                                                                         5   CN                                                                        6   CH.sub.3                                                                  7   CH.sub.2 CH.sub.3                                                         8   n-C.sub.3 H.sub.7                                                         9   i-C.sub.3 H.sub.7                                                         10  n-C.sub.4 H.sub.9                                                         11  i-C.sub.4 H.sub.9                                                         12  s-C.sub.4 H.sub.9                                                         13  t-C.sub.4 H.sub.9                                                         14  n-C.sub.5 H.sub.11                                                        15  n-C.sub.6 H.sub.13                                                        16  n-C.sub.7 H.sub.15                                                        17  n-C.sub.8 H.sub.17                                                        18  n-C.sub.9 H.sub.19                                                        19  n-C.sub.10 H.sub.21                                                       20  cyclopropyl                                                               21  1-methyl-cycloprop-1-yl                                                   22  cyclobutyl                                                                23  cyclopentyl                                                               24  cyclohexyl                                                                25  cyclohex-1-en-1-yl                                                        26  methoxymethyl                                                             27  ethoxymethyl                                                              28  phenoxymethyl                                                             29  benzyloxymethyl                                                           30  phenylmethyl                                                              31  morpholino-N-methyl                                                       32  phenylthiomethyl                                                          33  2-methylphenyl                                                            34  3-methylphenyl                                                            35  4-methylphenyl                                                            36  2-chlorophenyl                                                            37  3-chlorophenyl                                                            38  4-chlorophenyl                                                            39  2-bromophenyl                                                             40  3-bromophenyl                                                             41  4-bromophenyl                                                             42  2-fluorophenyl                                                            43  3-fluorophenyl                                                            44  4-fluorophenyl                                                            45  2-iodophenyl                                                              46  3-iodophenyl                                                              47  4-iodophenyl                                                              48  2-methoxyphenyl                                                           49  3-methoxyphenyl                                                           50  4-methoxyphenyl                                                           51  2-ethoxyphenyl                                                            52  3-ethoxyphenyl                                                            53  4-ethoxyphenyl                                                            54  2-n-propoxyphenyl                                                         55  3-n-propoxyphenyl                                                         56  4-n-propoxyphenyl                                                         57  2-i-propoxyphenyl                                                         58  3-i-propoxyphenyl                                                         59  4-i-propoxyphenyl                                                         60  2-n-butoxyphenyl                                                          61  3-n-butoxyphenyl                                                          62  4-n-butoxyphenyl                                                          63  2-sec.-butoxyphenyl                                                       64  3-sec.-butoxyphenyl                                                       65  4-sec.-butoxyphenyl                                                       66  2-iso-butoxyphenyl                                                        67  3-isobutoxyphenyl                                                         68  4-isobutoxyphenyl                                                         69  2-tert.-butoxyphenyl                                                      70  3-tert.-butoxyphenyl                                                      71  4-tert.-butoxyphenyl                                                      72  2-ethylphenyl                                                             73  3-ethylphenyl                                                             74  4-ethylphenyl                                                             75  2-n-propylphenyl                                                          76  3-n-propylphenyl                                                          77  4-n-propylphenyl                                                          78  2-i-propylphenyl                                                          79  3-i-propylphenyl                                                          80  4-i-propylphenyl                                                          81  2-n-butylphenyl                                                           82  3-n-butylphenyl                                                           83  4-n-butylphenyl                                                           84  2-isobutylphenyl                                                          85  3-isobutylphenyl                                                          86  4-isobutylphenyl                                                          87  2-sec.-butylphenyl                                                        88  3-sec.-butylphenyl                                                        89  4-sec.-butylphenyl                                                        90  2-tert.-butylphenyl                                                       91  3-tert.-butylphenyl                                                       92  4-tert.-butylphenyl                                                       93  2-NO.sub.2 -phenyl                                                        94  3-NO.sub.2 -phenyl                                                        95  4-NO.sub.2 -phenyl                                                        96  2-CF.sub.3 -phenyl                                                        97  3-CF.sub.3 -phenyl                                                        98  4-CF.sub.3 -phenyl                                                        99  2-CN-phenyl                                                              100  3-CN-phenyl                                                              101  4-CN-phenyl                                                              102  2-(CH.sub.2 CN)-phenyl                                                   103  3-(CH.sub.2 CN)-phenyl                                                   104  4-(CH.sub.2 CN)-phenyl                                                   105  2-CH.sub.3 CO-phenyl                                                     106  3-CH.sub.3 CO-phenyl                                                     107  4-CH.sub. 3 CO-phenyl                                                    108  2-CHO-phenyl                                                             109  3-CHO-phenyl                                                             110  4-CHO-phenyl                                                             111  2-NMe.sub.2 -phenyl                                                      112  3-NMe.sub.2 -phenyl                                                      113  4-NMe.sub.2 -phenyl                                                      114  2-CO.sub.2 Me-phenyl                                                     115  3-CO.sub.2 Me-phenyl                                                     116  4-CO.sub.2 Me-phenyl                                                     117  2-CO.sub.2 Et-phenyl                                                     118  3-CO.sub.2 Et-phenyl                                                     119  4-CO.sub.2 Et-phenyl                                                     120  2-OCF.sub.3 -phenyl                                                      121  3-OCF.sub.3 -phenyl                                                      122  4-OCF.sub.3 -phenyl                                                      123  2-phenyl-phenyl                                                          124  3-phenyl-phenyl                                                          125  4-phenyl-phenyl                                                          126  2-phenoxy-phenyl                                                         127  3-phenoxy-phenyl                                                         128  4-phenoxy-phenyl                                                         129  3,4-OCH.sub.2 O-phenyl                                                   130  3,4-OCH.sub.2 CH.sub.2 -phenyl                                           131  3,4,5-(OCH.sub.3).sub.3 -phenyl                                          132  3,4-(OCH.sub.3).sub.2 -phenyl                                            133  2,3-Me.sub.2 -phenyl                                                     134  2,4-Me.sub.2 -phenyl                                                     135  2,5-Me.sub.2 -phenyl                                                     136  2,6-Me.sub.2 -phenyl                                                     137  3,4-Me.sub.2 -phenyl                                                     138  3,5-Me.sub.2 -phenyl                                                     139  2,4,6-Me.sub.3 -phenyl                                                   140  2,3-Cl.sub.2 -phenyl                                                     141  2,4-Cl.sub.2 -phenyl                                                     142  2,5-Cl.sub.2 -phenyl                                                     143  2,6-Cl.sub.2 -phenyl                                                     144  3,4-Cl.sub.2 -phenyl                                                     145  3,5-Cl.sub.2 -phenyl                                                     146  2-methyl, 5-NO.sub.2 -phenyl                                             147  2-methyl, 3-NO.sub.2 -phenyl                                             148  2-methyl, 4-F-phenyl                                                     149  4-methyl, 3-F-phenyl                                                     150  2,6-Cl.sub.2, 4-NO.sub.2 -phenyl                                         151  2-NO.sub.2, 4-Cl-phenyl                                                  152  2-Cl, 5-CF.sub.3 -phenyl                                                 153  4-Cl, 3-CF.sub.3 -phenyl                                                 154  2-methyl, 4-CH.sub.3 CO-phenyl                                           155  2-methyl, 5-CH.sub.3 CO-phenyl                                           156  2,5-Me.sub.2, 4-CH.sub.3 CO-phenyl                                       157  2-Me, 4-methoximinomethyl-phenyl                                         158  2-Me, 5-methoximinomethyl-phenyl                                         159  2,5-Me.sub.2, 4-methoximinomethyl-phenyl                                 160  2-Me, 4-ethoximinomethyl-phenyl                                          161  2-Me, 4-n-propoximinomethyl-phenyl                                       162  2-Me, 4-i-propoximinomethyl-phenyl                                       163  2-Me, 4-n-butoximinomethyl-phenyl                                        164  2-Me, 5-ethoximinomethyl-phenyl                                          165  2,5-Me.sub.2, 4-ethoximinomethylphenyl                                   166  3-(5-phenyl-1,3,4-oxadiazol-2-yl)-                                            phenyl                                                                   167  3-(5-naphthyl-1,3,4-oxa-                                                      diazol-2-yl)-phenyl                                                      168  2-pyridyl                                                                169  3-pyridyl                                                                170  4-pyridyl                                                                171  5-methyl-2-pyridyl                                                       172  6-methyl-2-pyridyl                                                       173  quinolin-3-yl                                                            174  2,8(CF.sub.3).sub.2 -quinolin-4-yl                                       175  Isoquinolin-4-yl                                                         176  thien-2-yl                                                               177  thien-3-yl                                                               178  2-chloro-thien-3-yl                                                      179  2-chloro-thien-4-yl                                                      180  3-chloro-thien-2-yl                                                      181  2-chloro-thien-5-yl                                                      182  2,5-Cl.sub.2 -thien-3-yl                                                 183  3-furyl                                                                  184  2-(isoxazol-3-yl)-thien-5-yl                                             185  2-cyano-thien-3-yl                                                       186  3-Me-thien-2-yl                                                          187  2-NO.sub.2 -thien-5-yl                                                   188  3-benzothienyl                                                           189  3,5-Me.sub.2 -isoxazol-3-yl                                              190  2-thiazolyl                                                              191  5-NO.sub.2 -thiazol-2-yl                                                 192  5-NO.sub.2 -imidazol-4-yl                                                193  4-pyrrazolyl                                                             194  3,5-Me.sub.2 -pyrrazol-4-yl                                              195  3-(4-Cl-phenyl)-isoxazol-5-yl                                                                        107-110°  C.                               196  4-chloro-3-(3-chlorophenyl)-                                                  isoxazol-5-yl                                                            197  5-(4-methylphenyl)-1,3,4-                                                     oxadiazol-2-yl                                                           198  5-phenyl-1,3,4-thiadiazol-2-yl                                           199  3-(4-chlorophenyl)-1,2,4-                                                     oxadiazol-5-yl                                                           200  3-isopropyl-isoxazol-5-yl                                                201  5-(4-F-phenyl)-isoxazol-3-yl                                             202  4-ethyl-5-phenyl-isoxazol-3-yl                                           203  4-chloro-5-(3-Cl-phenyl)-                                                     isoxazol-3-yl                                                            204  CH.sub.2 Br                                                              205  CH.sub.2 Cl                                                              206  CH.sub.2 I                                                               207  1-naphthyl                                                               208  2-naphthyl                                                               209  6-methoxy-napht-2-yl                                                     ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                         ##STR18##                                                                                                phys. data                                                                    (m.p. [°C.]);                                                          IR [cm.sup.-1 ];                                  No.  R                      .sup.1 H-NMR [δ scale]                      ______________________________________                                         1   H                      3.17 (CH); 3.87;                                                              4.07 (Me);                                                                    7.27-7.60                                                                     (aryl)                                             2   SiMe.sub.3             0.22;                                                                         3.86; 4.06 (Me);                                                              7.25-7.61                                                                     (aryl)                                             3   SnMe.sub.3                                                                4   I                                                                         5   CN                                                                        6   CH.sub.3                                                                  7   CH.sub.2 CH.sub.3                                                         8   n-C.sub.3 H.sub.7                                                         9   i-C.sub.3 H.sub.7                                                         10  n-C.sub.4 H.sub.9                                                         11  i-C.sub.4 H.sub.9                                                         12  s-C.sub.4 H.sub.9                                                         13  t-C.sub.4 H.sub.9                                                         14  n-C.sub.5 H.sub.11                                                        15  n-C.sub.6 H.sub.13                                                        16  n-C.sub.7 H.sub.15                                                        17  n-C.sub.8 H.sub.17                                                        18  n-C.sub.9 H.sub.19                                                        19  n-C.sub.10 H.sub.21                                                       20  cyclopropyl                                                               21  1-methyl-cycloprop-1-yl                                                   22  cyclobutyl                                                                23  cyclopentyl                                                               24  cyclohexyl             1.23-2.61                                                                     (cyclohexyl);                                                                 3.85; 4.05 (Me);                                                              7.22-7.48                                                                     (aryl)                                             25  cyclohex-1-en-1-yl      98-100° C.                                 26  methoxymethyl          3.41; 3.87; 4.07                                                              (Me); 4.28                                                                    (CH.sub.2); 7.28-                                                             7.55 (aryl)                                        27  ethoxymethyl                                                              28  phenoxymethyl                                                             29  benzyloxymethyl                                                           30  phenylmethyl                                                              31  morpholino-N-methyl    2.59; 3.49; 3.76                                                              (CH.sub.2); 3.87;                                                             4.07 (Me); 7.23-                                                              7.71 (aryl)                                        32  phenylthiomethyl                                                          33  3-methyl-phenyl         95-99° C.                                  34  3-chloro-phenyl        3.86; 4.09 (Me);                                                              7.25-7.63                                                                     (aryl)                                             35  4-chloro-phenyl          91-96° C.                                 36  3-bromo-phenyl                                                            37  3-fluorophenyl                                                            38  4-fluorophenyl                                                            39  2-iodo-phenyl                                                             40  3-iodo-phenyl                                                             41  4-iodo-phenyl                                                             42  3-methoxy-phenyl       3.82; 3.84; 4.08                                                              (Me); 6.87-7.63                                                               (aryl)                                             43  4-methoxy-phenyl       118-121° C.                                 44  2-ethoxy-phenyl                                                           45  3-ethoxy-phenyl                                                           46  4-ethoxy-phenyl        1.42; 3.84; 4.07                                                              (Me); 4.05                                                                    (CH.sub.2); 6.84-                                                             7.61 (aryl)                                        47  2-n-propoxy-phenyl                                                        48  3-n-propoxy-phenyl                                                        49  4-n-propoxy-phenyl                                                        50  2-i-propoxy-phenyl                                                        51  3-i-propoxy-phenyl     1.34; 3.87; 4.08                                                              (Me); 4.57                                                                    (CH); 6.75-                                                                   7.61 (aryl)                                        52  4-i-propoxy-phenyl                                                        53  2-n-butoxy-phenyl                                                         54  3-n-butoxy-phenyl                                                         55  4-n-butoxy-phenyl                                                         56  2-sec.-butoxy-phenyl                                                      57  3-sec.-butoxy-phenyl                                                      58  4-sec.-butoxy-phenyl                                                      59  2-iso-butoxy-phenyl                                                       60  3-iso-butoxy-phenyl                                                       61  4-iso-butoxy-phenyl                                                       62  2-tert.-butoxyphenyl                                                      63  3-tert.-butoxyphenyl                                                      64  4-tert.-butoxyphenyl                                                      65  2-ethyl-phenyl                                                            66  3-ethyl-phenyl                                                            67  4-ethyl-phenyl         1.23; 3.84; 4.09                                                              (Me); 2.65                                                                    (CH.sub.2); 7.17-                                                             7.63 (aryl)                                        68  2-n-propyl-phenyl                                                         69  3-n-propyl-phenyl                                                         70  4-n-propyl-phenyl                                                         71  2-i-propyl-phenyl                                                         72  3-i-propyl-phenyl                                                         73  4-i-propyl-phenyl      1.24; 3.85; 4.09                                                              (Me); 2.91                                                                    (CH); 7.20-                                                                   7.61 (aryl)                                        74  2-n-butylphenyl                                                           75  3-n-butylphenyl                                                           76  4-n-butylphenyl                                                           77  2-iso-butyl-phenyl                                                        78  3-iso-butyl-phenyl                                                        79  4-iso-butyl-phenyl                                                        80  2-sec.-butylphenyl                                                        81  3-sec.-butylphenyl                                                        82  4-sec.-butylphenyl                                                        83  2-tert.-butylphenyl                                                       84  3-tert.-butylphenyl                                                       85  4-tert.-butylphenyl    1.31; 3.85; 4.09                                                              (Me); 7.35-                                                                   7.61 (aryl)                                        86  3-NO.sub.2 -phenyl     122-125° C.                                 87  4-NO.sub.2 -phenyl     160-164° C.                                 88  2-CF.sub.3 -phenyl      66-70° C.                                  89  3-CF.sub.3 -phenyl     3.86; 4.09 (Me);                                                              7.33-7.73                                                                     (aryl)                                             90  2-CN-phenyl                                                               91  3-CN-phenyl                                                               92  4-CN-phenyl            145-149° C.                                 93  2-(CH.sub.2 CN)-phenyl 3.82; 4.04 (Me);                                                              3.92 (CH.sub.2);                                                              7.25-7.65                                                                     (aryl)                                             94  3-(CH.sub.2 CN)-phenyl 3.75 (CH.sub.2);                                                              3.84; 4.08 (Me);                                                              7.33-7.63 (aryl)                                   95  4-(CH.sub.2 CN)-phenyl  85-90° C.                                  96  2-CH.sub.3 CO-phenyl                                                      97  3-CH.sub.3 CO-phenyl                                                      98  4-CH.sub.3 CO-phenyl   121-123° C.                                 99  2-CHO-phenyl                                                             100  3-CHO-phenyl           3.87; 4.10 (Me);                                                              7.36-7.94;                                                                    (aryl; 10.01                                                                  (CH)                                              101  4-CHO-phenyl           104-106° C.                                102  2-NMe.sub.2 -phenyl                                                      103  3-NMe.sub.2 -phenyl                                                      104  4-NMe.sub.2 -phenyl    2.99; 3.82; 4.06                                                              (Me);                                                                         6.59-7.55                                                                     (aryl)                                            105  2-CO.sub.2 Me-phenyl                                                     106  3-CO.sub.2 Me-phenyl   3.86; 3.94; 4.09                                                              (Me);                                                                         7.35-8.14                                                                     (aryl)                                            107  4-CO.sub.2 Me-phenyl                                                     108  2-CO.sub.2 Et-phenyl                                                     109  3-CO.sub.2 Et-phenyl                                                     110  4-CO.sub.2 Et-phenyl                                                     111  2-OCF.sub.3 -phenyl                                                      112  3-OCF.sub.3 -phenyl                                                      113  4-OCF.sub.3 -phenyl                                                      114  2-phenyl-phenyl        3.79; 4.01 (Me);                                                              7.23-7.61                                                                     (aryl)                                            115  3-phenyl-phenyl        3.85; 4.09 (Me);                                                              7.38-7.73 (aryl)                                  116  4-phenyl-phenyl        137-142° C.                                117  2-phenoxy-phenyl                                                         118  3-phenoxy-phenyl                                                         119  4-phenoxy-phenyl       3.82; 4.07 (Me);                                                              6.92-7.58                                                                     (aryl)                                            120  3,4-OCH.sub.2 O-phenyl 3.84; 4.07 (Me);                                                              5.98 (CH.sub.2);                                                              6.76-7.58                                                                     (aryl)                                            121  3,4-OCH.sub.2 CH.sub.2 O-phenyl                                                                      3.84; 4.07 (Me);                                                              4.25 (CH.sub.2);                                                              6.79-7.58                                                                     (aryl)                                            122  3,4,5-(OCH.sub.3).sub.3 -phenyl                                                                      3.86; 3.88;                                                                   3.89; 3.92;                                                                   4.10 (Me);                                                                    6.75-7.61                                                                     (aryl)                                            123  3,4-(OCH.sub.3).sub.2 -phenyl                                            124  2,3-Me.sub.2 -phenyl   105-109° C.                                125  2,4-Me.sub.2 -phenyl   104-109° C.                                126  2,5-Me.sub.2 -phenyl   142-147° C.                                127  2,6-Me.sub.2 -phenyl                                                     128  3,4-Me.sub.2 -phenyl    86-89° C.                                 129  3,5-Me.sub.2 -phenyl   2.30 (2x); 3.84;                                                              4.08 (Me);                                                                    6.97-7.61 (aryl)                                  130  2,4,6-Me.sub.3 -phenyl 108-112° C.                                131  2,3-Cl.sub.2 -phenyl   117-121° C.                                132  2,4-Cl.sub.2 -phenyl   113-116° C.                                133  2,5-Cl.sub.2 -phenyl   107-110° C.                                134  2,6-Cl.sub.2 -phenyl   145-148° C.                                135  3,4-Cl.sub.2 -phenyl    93-96° C.                                 136  3,5-Cl.sub.2 -phenyl   106-109° C.                                137  2-methyl, 5-NO.sub.2 -phenyl                                             138  2-methyl, 3-NO.sub.2 -phenyl                                             139  2-methyl, 4-F-phenyl                                                     140  4-methyl, 3-F-phenyl                                                     141  2,6-Cl.sub.2, 4-NO.sub.2 -phenyl                                         142  2-NO.sub.2, 4-Cl-phenyl                                                  143  2-Cl, 5-CF.sub.3 -phenyl                                                                             3.87; 4.07 (Me);                                                              7.35-8.37 (aryl)                                  144  4-Cl, 3-CF.sub.3 -phenyl                                                 145  2-methyl, 4-CH.sub.3 CO-phenyl                                           146  2-methyl, 5-CH.sub.3 CO-phenyl                                           147  2,5-Me.sub.2, 4-CH.sub.3 CO-phenyl                                       148  2-Me, 4-methoximinomethyl-phenyl                                                                     2.22; 2.46;                                                                   3.86; 4.01;                                                                   4.09 (Me);                                                                    7.20-7.75                                                                     (aryl)                                            149  2-Me, 5-methoximinomethyl-phenyl                                                                     2.22; 2.45;                                                                   3.84; 3.99; 4.06                                                              (Me); 7.17-7.71                                                               (aryl)                                            150  2,5-Me.sub.2, 4-methoximinomethyl-phenyl                                 151  2-Me, 4-ethoximinomethyl-phenyl                                          152  2-Me, 4-n-propoximinomethyl-phenyl                                       153  2-Me, 4-i-propoximinomethyl-phenyl                                       154  2-Me, 4-n-butoximinomethyl-phenyl                                        155  2-Me, 5-ethoximinomethyl-phenyl                                          156  2,5-Me.sub.2, 4-ethoximinomethyl-phenyl                                  157  1-Me-2-naphthyl                                                          158  1-naphthyl             3.82; 4.09 (Me);                                                              7.35-8.37 (aryl)                                  159  2-naphthyl             114-118° C.                                160  6-methoxy-2-naphthyl   3.86; 3.95; 4.11                                                              (Me); 7.12-                                                                   7.94 (aryl)                                       161                                                                                 ##STR19##             2240 (CC, RA-MAN)                                 162                                                                                 ##STR20##             1725; 1441; 1258; 1209; 1069; 1037; 1013;                                     950                                                     ##STR21##                                                               163                                                                                 ##STR22##             1727; 1437; 1324; 1309; 1264; 1215; 1069;                                     1040                                                    ##STR23##                                                               164  3-(5-phenyl-1,3,4-oxadiazol-2-yl)-                                                                    44-52° C.                                      phenyl                                                                   165  3-(5-naphthyl-1,3,4-oxa-                                                      diazol-2-yl)-phenyl                                                      166  2-pyridyl              3.87; 4.09 (Me);                                                              7.22-8.62                                                                     (8H)                                              167  3-pyridyl               78-82° C.                                 168  4-pyridyl                                                                169  5-methyl-2-pyridyl                                                       170  6-methyl-2-pyridyl                                                       171  quinolin-3-yl                                                            172  2,8(CF.sub.3).sub.2 -quinolin-4-yl                                       173  isoquinolin-4-yl                                                         174  thien-2-yl             3.87; 4.09 (Me);                                                              6.95-7.58                                                                     (aryl)                                            175  thien-3-yl              80-89° C.                                 176  2-chloro-thien-3-yl                                                      177  2-chloro-thien-4-yl    3.84; 4.07 (Me);                                                              6.98-7.58                                                                     (aryl)                                            178  3-chloro-thien-2-yl    3.88; 4.09 (Me);                                                              6.93-7.66                                                                     (aryl)                                            179  2-chloro-thien-5-yl    3.87; 4.08 (Me);                                                              6.81-7.59                                                                     (aryl)                                            180  2,5-Cl.sub.2 -thien-3-yl                                                 181  3-furyl                                                                  182  2-(isoxazol-3-yl)-thien-5-yl                                             183  2-cyano-thien-3-yl                                                       184  3-Me-thien-2-yl                                                          185  2-NO.sub.2 -thien-5-yl                                                   186  3-benzothienyl                                                           187  3,5-Me.sub.2 -isoxazol-3-yl                                              188  2-thiazolyl                                                              189  5-NO.sub.2 -thiazol-2-yl                                                 190  5-NO.sub.2 -imidazol-4-yl                                                191  4-pyrrazolyl                                                             192  3,5-Me.sub.2 -pyrrazol-4-yl                                              193  3-(4-Cl-phenyl)-isoxazol-5-yl                                            194  4-chloro-3-(3-chlorophenyl)-                                                  isoxazol-5-yl                                                            195  5-(4-methylphenyl)-1,3,4-                                                     oxadiazol-2-yl                                                           196  5-phenyl-1,3,4-thiadiazol-2-yl                                           197  3-(4-chlorophenyl)-1,2,4-                                                     oxadiazol-5-yl                                                           198  3-isopropyl-isoxazol-5-yl                                                199  5-(4-F-phenyl)-isoxazol-3-yl                                             200  4-ethyl-5-phenyl-isoxazol-3-yl                                           201  4-chloro-5-(3-Cl-phenyl)-iso-                                                 oxalzol-3-yl                                                             202  CH.sub.2 Br                                                              203  CH.sub.2 Cl                                                              204  CH.sub.2 I                                                               205  9-anthracenyl          159-164° C.                                206  2-methoxy-naphth-1-yl  129-137° C.                                207  CHCH-phenyl             97-102° C.                                208  4-(benzthiazol-2-yl)-phenyl                                                                          164-168° C.                                209  1-pyrenyl              179-183° C.                                ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                         ##STR24##                                                                                                phys. data                                                                    (m.p. [°C.]);                                                          IR [cm.sup.-1 ];                                  No.  R                      .sup.1 H-NMR [δ scale]                      ______________________________________                                         1   H                                                                         2   SiMe.sub.3                                                                3   SnMe.sub.3                                                                4   I                                                                         5   CN                                                                        6   CH.sub.3                                                                  7   CH.sub.2 CH.sub.3                                                         8   n-C.sub.3 H.sub.7                                                         9   i-C.sub.3 H.sub.7                                                         10  n-C.sub.4 H.sub.9                                                         11  i-C.sub.4 H.sub.9                                                         12  s-C.sub.4 H.sub.9                                                         13  t-C.sub.4 H.sub.9                                                         14  n-C.sub.5 H.sub.11                                                        15  n-C.sub.6 H.sub.13                                                        16  n-C.sub.7 H.sub.15                                                        17  n-C.sub.8 H.sub.17                                                        18  n-C.sub.9 H.sub.19                                                        19  n-C.sub.10 H.sub.21                                                       20  cyclopropyl                                                               21  1-methyl-cycloprop-1-yl                                                   22  cyclobutyl                                                                23  cyclopentyl                                                               24  cyclohexyl                                                                25  cyclohex-1-en-1-yl                                                        26  methoxymethyl                                                             27  ethoxymethyl                                                              28  phenoxymethyl                                                             29  benzyloxymethyl                                                           30  phenylmethyl                                                              31  morpholino-N-methyl                                                       32  phenylthiomethyl                                                          33  3-methyl-phenyl                                                           34  3-chloro-phenyl                                                           35  4-chloro-phenyl                                                           36  3-bromo-phenyl                                                            37  3-fluorophenyl                                                            38  4-fluorophenyl                                                            39  2-iodo-phenyl                                                             40  3-iodo-phenyl                                                             41  4-iodo-phenyl                                                             42  3-methoxy-phenyl                                                          43  4-methoxy-phenyl                                                          44  2-ethoxy-phenyl                                                           45  3-ethoxy-phenyl                                                           46  4-ethoxy-phenyl                                                           47  2-n-propoxy-phenyl                                                        48  3-n-propoxy-phenyl                                                        49  4-n-propoxy-phenyl                                                        50  2-i-propoxy-phenyl                                                        51  3-i-propoxy-phenyl                                                        52  4-i-propoxy-phenyl                                                        53  2-n-butoxy-phenyl                                                         54  3-n-butoxy-phenyl                                                         55  4-n-butoxy-phenyl                                                         56  2-sec.-butoxy-phenyl                                                      57  3-sec.-butoxy-phenyl                                                      58  4-sec.-butoxy-phenyl                                                      59  2-iso-butoxy-phenyl                                                       60  3-iso-butoxy-phenyl                                                       61  4-iso-butoxy-phenyl                                                       62  2-tert.-butoxyphenyl                                                      63  3-tert.-butoxyphenyl                                                      64  4-tert.-butoxyphenyl                                                      65  2-ethyl-phenyl                                                            66  3-ethyl-phenyl                                                            67  4-ethyl-phenyl                                                            68  2-n-propyl-phenyl                                                          69 3-n-propyl-phenyl                                                         70  4-n-propyl-phenyl                                                         71  2-i-propyl-phenyl                                                         72  3-i-propyl-phenyl                                                         73  4-i-propyl-phenyl                                                         74  2-n-butylphenyl                                                           75  3-n-butylphenyl                                                           76  4-n-butylphenyl                                                           77  2-iso-butyl-phenyl                                                        78  3-iso-butyl-phenyl                                                        79  4-iso-butyl-phenyl                                                        80  2-sec.-butylphenyl                                                        81  3-sec.-butylphenyl                                                        82  4-sec.-butylphenyl                                                        83  2-tert.-butylphenyl                                                       84  3-tert.-butylphenyl                                                       85  4-tert.-butylphenyl                                                       86  3-NO.sub.2 -phenyl                                                        87  4-NO.sub.2 -phenyl                                                        88  2-CF.sub.3 -phenyl                                                        89  3-CF.sub.3 -phenyl                                                        90  2-CN-phenyl                                                               91  3-CN-phenyl                                                               92  4-CN-phenyl                                                               93  2-(CH.sub.2 CN)-phenyl                                                    94  3-(CH.sub.2 CN)-phenyl                                                    95  4-(CH.sub.2 CN)-phenyl                                                    96  2-CH.sub.3 CO-phenyl                                                      97  3-CH.sub.3 CO-phenyl                                                      98  4-CH.sub.3 CO-phenyl                                                      99  2-CHO-phenyl                                                             100  3-CHO-phenyl                                                             101  4-CHO-phenyl                                                             102  2-NMe.sub.2 -phenyl                                                      103  3-NMe.sub.2 -phenyl                                                      104  4-NMe.sub.2 -phenyl                                                      105  2-CO.sub.2 Me-phenyl                                                     106  3-CO.sub.2 Me-phenyl                                                     107  4-CO.sub.2 Me-phenyl                                                     108  2-CO.sub.2 Et-phenyl                                                     109  3-CO.sub.2 Et-phenyl                                                     110  4-CO.sub.2 Et-phenyl                                                     111  2-OCF.sub.3 -phenyl                                                      112  3-OCF.sub.3 -phenyl                                                      113  4-OCF.sub.3 -phenyl                                                      114  2-phenyl-phenyl                                                          115  3-phenyl-phenyl                                                          116  4-phenyl-phenyl                                                          117  2-phenoxy-phenyl                                                         118  3-phenoxy-phenyl                                                         119  4-phenoxy-phenyl                                                         120  3,4-OCH.sub.2 O-phenyl                                                   121  3,4-OCH.sub.2 CH.sub.2 -phenyl                                           122  3,4,5-(OCH.sub.3).sub.3 -phenyl                                          123  3,4-(OCH.sub.3).sub.2 -phenyl                                            124  2,3-Me.sub.2 -phenyl                                                     125  2,4-Me.sub.2 -phenyl                                                     126  2,5-Me.sub.2 -phenyl                                                     127  2,6-Me.sub.2 -phenyl                                                     128  3,4-Me.sub.2 -phenyl                                                     129  3,5-Me.sub.2 -phenyl                                                     130  2,4,6-Me.sub.3 -phenyl                                                   131  2,3-Cl.sub.2 -phenyl                                                     132  2,4-Cl.sub.2 -phenyl                                                     133  2,5-Cl.sub.2 -phenyl                                                     134  2,6-Cl.sub.2 -phenyl                                                     135  3,4-Cl.sub.2 -phenyl                                                     136  3,5-Cl.sub.2 -phenyl                                                     137  2-methyl, 5-NO.sub.2 -phenyl                                             138  2-methyl, 3-NO.sub.2 -phenyl                                             139  2-methyl, 4-F-phenyl                                                     140  4-methyl, 3-F-phenyl                                                     141  2,6-Cl.sub.2, 4-NO.sub.2 -phenyl                                         142  2-NO.sub.2, 4-Cl-phenyl                                                  143  2-Cl, 5-CF.sub.3 -phenyl                                                 144  4-Cl, 3-CF.sub.3 -phenyl                                                 145  2-methyl, 4-CH.sub.3 CO-phenyl                                           146  2-methyl, 5-CH.sub.3 CO-phenyl                                           147  2,5-Me.sub.2, 4-CH.sub.3 CO-phenyl                                       148  2-Me, 4-methoximinomethyl-phenyl                                         149  2-Me, 5-methoximinomethyl-phenyl                                         150  2,5-Me.sub.2, 4-methoximinomethyl-phenyl                                 151  2-Me, 4-ethoximinomethyl-phenyl                                          152  2-Me, 4-n-propoximinomethyl-phenyl                                       153  2-Me, 4-i-propoximinomethyl-phenyl                                       154  2-Me, 4-n-butoximinomethyl-phenyl                                        155  2-Me, 5-ethoximinomethyl-phenyl                                          156  2,5-Me.sub.2, 4-ethoximinomethyl-phenyl                                  157  1-Me-2-naphthyl                                                          158  1-naphthyl                                                               159  2-naphthyl                                                               160  6-methoxy-2-naphthyl                                                     161  3-(5-phenyl-1,3,4-oxadiazol-2-yl)-                                            phenyl                                                                   162  3-(5-naphthyl-1,3,4-oxa-                                                      diazol-2-yl)-phenyl                                                      163  2-pyridyl                                                                164  3-pyridyl                                                                165  4-pyridyl                                                                166  5-methyl-2-pyridyl                                                       167  6-methyl-2-pyridyl                                                       168  quinolin-3-yl                                                            169  2,8(CF.sub.3).sub.2 -quinolin-4-yl                                       170  isoquinolin-4-yl                                                         171  thien-2-yl                                                               172  thien-3-yl                                                               173  2-chloro-thien-3-yl                                                      174  2-chloro-thien-4-yl                                                      175  3-chloro-thien-2-yl                                                      176  2-chloro-thien-5-yl                                                      177  2,5-Cl.sub.2 -thien-3-yl                                                 178  3-furyl                                                                  179  2-(isoxazol-3-yl)-thien-5-yl                                             180  2-cyano-thien-3-yl                                                       181  3-Me-thien-2-yl                                                          182  2-NO.sub.2 -thien-5-yl                                                   183  3-benzothienyl                                                           184  3,5-Me.sub.2 -isoxazol-3-yl                                              185  2-thiazolyl                                                              186  5-NO.sub.2 -thiazol-2-yl                                                 187  5-NO.sub.2 -imidazol-4-yl                                                188  4-pyrrazolyl                                                             189  3,5-Me.sub.2 -pyrrazol-4-yl                                              190  5-NO.sub.2 -imidazol-4-yl                                                191  3-(4-Cl-phenyl)-isoxazol-5-yl                                            192  4-chloro-3-(3-chlorophenyl)-                                                  isoxazol-5-yl                                                            193  5-(4-methylphenyl)-1,3,4-                                                     oxadiazol-2-yl                                                           194  5-phenyl-1,3,4-thiadiazol-2-yl                                           195  3-(4-chlorophenyl)-1,2,4-                                                     oxadiazol-5-yl                                                           196  3-isopropyl-isoxazol-5-yl                                                197  5-(4-F-phenyl)-isoxazol-3-yl                                             198  4-ethyl-5-phenyl-isoxazol-3-yl                                           199  4-chloro-5-(3-Cl-phenyl)-                                                     isooxazol-3-yl                                                           200  CH.sub.2 Br                                                              201  CH.sub.2 Cl                                                              202  CH.sub.2 I                                                               ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                         ##STR25##                                                                                                phys. data                                                                    (m.p. [°C.]);                                                          IR [cm.sup.-1 ];                                  No.  R                      .sup.1 H-NMR [δ scale]                      ______________________________________                                         1   H                      2.99; 3.98 (Me);                                                              3.13 (H); 6.80                                                                (NH); 7.21-7.58                                                               (aryl)                                             2   SiMe.sub.3                                                                3   SnMe.sub.3                                                                4   I                                                                         5   CN                                                                        6   CH.sub.2 CH.sub.3                                                         7   n-C.sub.3 H.sub.7                                                         8   i-C.sub.3 H.sub.7                                                         9   n-C.sub.4 H.sub.9                                                         10  i-C.sub.4 H.sub.9                                                         11  s-C.sub.4 H.sub.9                                                         12  t-C.sub.4 H.sub.9                                                         13  n-C.sub.5 H.sub.11                                                        14  n-C.sub.6 H.sub.13                                                        15  n-C.sub.7 H.sub.15                                                        16  n-C.sub.8 H.sub.17                                                        17  n-C.sub.9 H.sub.19                                                        18  n-C.sub.10 H.sub.21                                                       19  cyclopropyl                                                               20  1-methyl-cycloprop-1-yl                                                   21  cyclobutyl                                                                22  cyclopentyl                                                               23  cyclohexyl                                                                24  cyclohex-1-en-1-yl                                                        25  methoxymethyl                                                             26  ethoxymethyl                                                              27  phenoxymethyl                                                             28  benzyloxymethyl                                                           29  phenylmethyl                                                              30  morpholino-N-methyl                                                       31  phenylthiomethyl                                                          32  2-methyl-phenyl        128-129° C.                                 33  3-methyl-phenyl                                                           34  4-methyl-phenyl                                                           35  2-chloro-phenyl                                                           36  3-chloro-phenyl                                                           37  4-chloro-phenyl                                                           38  2-bromo-phenyl                                                            39  3-bromo-phenyl                                                            40  3-bromo-phenyl                                                            41  2-fluorophenyl                                                            42  3-fluorophenyl                                                            43  4-fluorophenyl                                                            44  2-iodo-phenyl                                                             45  3-iodo-phenyl                                                             46  4-iodo-phenyl                                                             47  2-methoxy-phenyl                                                          48  3-methoxy-phenyl                                                          49  4-methoxy-phenyl                                                          50  2-ethoxy-phenyl                                                           51  3-ethoxy-phenyl                                                           52  4-ethoxy-phenyl                                                           53  2-n-propoxy-phenyl                                                        54  3-n-propoxy-phenyl                                                        55  4-n-propoxy-phenyl                                                        56  2-i-propoxy-phenyl                                                        57  3-i-propoxy-phenyl                                                        58  4-i-propoxy-phenyl                                                        59  2-n-butoxy-phenyl                                                         60  3-n-butoxy-phenyl                                                         61  4-n-butoxy-phenyl                                                         62  2-sec.-butoxy-phenyl                                                      63  3-sec.-butoxy-phenyl                                                      64  4-sec.-butoxy-phenyl                                                      65  2-iso-butoxy-phenyl                                                       66  3-iso-butoxy-phenyl                                                       67  4-iso-butoxy-phenyl                                                       68  2-tert.-butoxyphenyl                                                      69  3-tert.-butoxyphenyl                                                      70  4-tert.-butoxyphenyl                                                      71  2-ethyl-phenyl                                                            72  3-ethyl-phenyl                                                            73  4-ethyl-phenyl                                                            74  2-n-propyl-phenyl                                                         75  3-n-propyl-phenyl                                                         76  4-n-propyl-phenyl                                                         77  2-i-propyl-phenyl                                                         78  3-i-propyl-phenyl                                                         79  4-i-propyl-phenyl                                                         80  2-n-butylphenyl                                                           81  3-n-butylphenyl                                                           82  4-n-butylphenyl                                                           83  2-iso-butyl-phenyl                                                        84  3-iso-butyl-phenyl                                                        85  4-iso-butyl-phenyl                                                        86  2-sec.-butylphenyl                                                        87  3-sec.-butylphenyl                                                        88  4-sec.-butylphenyl                                                        89  2-tert.-butylphenyl                                                       90  3-tert.-butylphenyl                                                       91  4-tert.-butylphenyl                                                       92  2-NO.sub.2 -phenyl                                                        93  3-NO.sub.2 -phenyl                                                        94  4-NO.sub.2 -phenyl                                                        95  2-CF.sub.3 -phenyl                                                        96  3-CF.sub.3 -phenyl     139-144° C.                                 97  4-CF.sub.3 -phenyl                                                        98  2-CN-phenyl                                                               99  3-CN-phenyl                                                              100  4-CN-phenyl                                                              101  2-(CH.sub.2 CN)-phenyl 147-151° C.                                102  3-(CH.sub.2 C N)-phenyl                                                  103  4-(CH.sub.2 CN)-phenyl                                                   104  2-CH.sub.3 CO-phenyl                                                     105  3-CH.sub.3 CO-phenyl                                                     106  4-CH.sub.3 CO-phenyl                                                     107  2-CHO-phenyl                                                             108  3-CHO-phenyl                                                             109  4-CHO-phenyl                                                             110  2-NMe.sub.2 -phenyl                                                      111  3-NMe.sub.2 -phenyl                                                      112  4-NMe.sub.2 -phenyl                                                      113  2-CO.sub.2 Me-phenyl                                                     114  3-CO.sub.2 Me-phenyl                                                     115  4-CO.sub.2 Me-phenyl                                                     116  2-CO.sub.2 Et-phenyl                                                     117  3-CO.sub.2 Et-phenyl                                                     118  4-CO.sub.2 Et-phenyl                                                     119  2-OCF.sub.3 -phenyl                                                      120  3-OCF.sub.3 -phenyl                                                      121  4-OCF.sub.3 -phenyl                                                      122  2-phenyl-phenyl                                                          123  3-phenyl-phenyl                                                          124  4-phenyl-phenyl                                                          125  2-phenoxy-phenyl                                                         126  3-phenoxy-phenyl                                                         127  4-phenoxy-phenyl                                                         128  3,4-OCH.sub.2 O-phenyl                                                   129  3,4-OCH.sub.2 CH.sub.2 -phenyl                                           130  3,4,5-(OCH.sub.3).sub.3 -phenyl                                          131  3,4-(OCH.sub.3).sub.2 -phenyl                                            132  2,3-Me.sub.2 -phenyl                                                     133  2,4-Me.sub.2 -phenyl                                                     134  2,5-Me.sub.2 -phenyl                                                     135  2,6-Me.sub.2 -phenyl                                                     136  3,4-Me.sub.2 -phenyl                                                     137  3,5-Me.sub.2 -phenyl                                                     138  2,4,6-Me.sub.3 -phenyl                                                   139  2,3-Cl.sub.2 -phenyl   130-132° C.                                140  2,4-Cl.sub.2 -phenyl   143-145°  C.                               141  2,5-Cl.sub.2 -phenyl   134-137° C.                                142  2,6-Cl.sub.2 -phenyl                                                     143  3,4-Cl.sub.2 -phenyl   147-150° C.                                144  3,5-Cl.sub.2 -phenyl   159-163° C.                                145  2-methyl, 5-NO.sub.2 -phenyl                                             146  2-methyl, 3-NO.sub.2 -phenyl                                             147  2-methyl, 4-F-phenyl                                                     148  4-methyl, 3-F-phenyl                                                     149  2,6-Cl.sub.2, 4-NO.sub.2 -phenyl                                         150  2-NO.sub.2, 4-Cl-phenyl                                                                              192° C.                                    151  2-Cl, 5-CF.sub.3 -phenyl                                                 152  4-Cl, 3-CF.sub.3 -phenyl                                                 153  2-methyl, 4-CH.sub.3 CO-phenyl                                           154  2-methyl, 5-CH.sub.3 CO-phenyl                                           155  2,5-Me.sub.2, 4-CH.sub.3 CO-phenyl                                       156  2-Me, 4-methoximinomethyl-phenyl                                                                     136-140° C.                                157  2-Me, 5-methoximinomethyl-phenyl                                                                     2,12; 2,45; 2,93;                                                             3,96; 3,99 (Me);                                                              6,79 (NH);                                                                    7,18-7,71 (Aryl)                                  158  2,5-Me.sub.2, 4-methoximinomethyl-phenyl                                 159  2-Me, 4-ethoximinomethyl-phenyl                                          160  2-Me, 4-n-propoximinomethyl-phenyl                                       161  2-Me, 4-i-propoximinomethyl-phenyl                                       162  2-Me, 4-n-butoximinomethyl-phenyl                                        163  2-Me, 5-ethoximinomethyl-phenyl                                          164  2,5-Me.sub.2, 4-ethoximinomethylphenyl                                   165  3-(5-phenyl-1,3,4-oxadiazol-2-yl)-                                            phenyl                                                                   166  3-(5-naphthyl-1,3,4-oxa-                                                      diazol-2-yl)-phenyl                                                      167  2-pyridyl                                                                168  3-pyridyl                                                                169  4-pyridyl                                                                170  5-methyl-2-pyridyl                                                       171  6-methyl-2-pyridyl                                                       172  quinolin-3-yl                                                            173  2,8(CF.sub. 3).sub.2 -quinolin-4-yl                                      174  isoquinolin-4-yl                                                         175  thien-2-yl                                                               176  thien-3-yl                                                               177  2-chloro-thien-3-yl                                                      178  2-chloro-thien-4-yl                                                      179  3-chloro-thien-2-yl                                                      180  2-chloro-thien-5-yl                                                      181  2,5-Cl.sub.2 -thien-3-yl                                                 182  3-furyl                                                                  183  2-(isoxazol-3-yl)-thien-5-yl                                             184  2-cyano-thien-3-yl                                                       185  3-Me-thien-2-yl                                                          186  2-NO.sub.2 -thien-5-yl                                                   187  3-benzothienyl                                                           188  3,5-Me.sub.2 -isoxazol-3-yl                                              189  2-Thiazolyl                                                              190  5-NO.sub.2 -thiazol-2-yl                                                 191  5-NO.sub.2 -imidazol-4-yl                                                192  4-pyrrazolyl                                                             193  3,5-Me.sub.2 -pyrrazol-4-yl                                              194  3-(4-Cl-phenyl)-isoxazol-5-yl                                            195  4-chloro-3-(3-chlorophenyl)-                                                  isoxazol-5-yl                                                            196  5-(4-methylphenyl)-1,3,4-                                                     oxadiazol-2-yl                                                           197  5-phenyl-1,3,4-thiadiazol-2-yl                                           198  3-(4-chlorophenyl)-1,2,4-                                                     oxadiazol-5-yl                                                           199  3-isopropyl-isoxazol-5-yl                                                200  5-(4-F-phenyl)-isoxazol-3-yl                                             201  4-ethyl-5-phenyl-isoxazol-3-yl                                           202  4-chloro-5-(3-Cl-phenyl)-                                                     isoxazol-3-yl                                                            203  CH.sub.2 Br                                                              204  CH.sub.2 Cl                                                              205  CH.sub.2 I                                                               206  1-naphthyl                                                               207  2-naphthyl             155-158° C.                                208  6-methoxy-naphth-2-yl                                                    209  CHCH-phenyl            109-112° C.                                ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                         ##STR26##                                                                                              phys. data                                                                    m.p. [°C.]                                                             IR [cm.sup.-1 ]                                     No.      R.sup.18         .sup.1 H-NMR [δ scale]                        ______________________________________                                         1       OH                                                                    2       O-methyl                                                              3       O-ethyl                                                               4       O-(n-propyl)                                                          5       O-(i-propyl)                                                          6       O-(n-butyl)                                                           7       O-(i-butyl)                                                           8       O-(s-butyl)                                                           9       O-(tert.-butyl)                                                      10       O-benzyl                                                             11       O-(2-methylbenzyl)                                                   12       O-(3-methylbenzyl)                                                   13       O-(4-methylbenzyl)                                                   14       O-(2-Cl-benzyl)                                                      15       O-(3-Cl-benzyl)                                                      16       O-(4-Cl-benzyl)                                                      17       methyl                                                               18       ethyl                                                                19       n-propyl                                                             20       i-propyl                                                             21       n-butyl                                                              22       i-butyl                                                              23       s-butyl                                                              24       tert.-butyl                                                          25       benzyl                                                               26       phenyl                                                               27       2-Me-phenyl                                                          28       3-Me-phenyl                                                          29       4-Me-phenyl                                                          30       2-F-phenyl                                                           31       3-F-phenyl                                                           32       4-F-phenyl                                                           33       2-Cl-phenyl                                                          34       3-Cl-phenyl                                                          35       4-Cl-phenyl                                                          36       2-Br-phenyl                                                          37       3-Br-phenyl                                                          38       4-Br-phenyl                                                          39       2-I-phenyl                                                           40       3-I-phenyl                                                           41       4-I-phenyl                                                           42       2-CF.sub.3 -phenyl                                                   43       3-CF.sub.3 -phenyl                                                   44       4-CF.sub.3 -phenyl                                                   45       2-OCH.sub.3 -phenyl                                                  46       3-OCH.sub.3 -phenyl                                                  47       4-OCH.sub.3 -phenyl                                                  48       2-CN-phenyl                                                          49       3-CN-phenyl                                                          50       4-CN-phenyl                                                          51       2-NO.sub.2 -phenyl                                                   52       3-NO.sub.2 -phenyl                                                   53       4-NO.sub.2 -phenyl                                                   54       2-OCF.sub.3 -phenyl                                                  55       3-OCF.sub.3 -phenyl                                                  56       4-OCF.sub.3 -phenyl                                                  57       2-CCl.sub.3 -phenyl                                                  58       3-CCl.sub.3 -phenyl                                                  59       4-CCl.sub.3 -phenyl                                                  60       2-NMe.sub.2 -phenyl                                                  61       3-NMe.sub.2 -phenyl                                                  62       4-NMe.sub.2 -phenyl                                                  63       2-tert.-butylphenyl                                                  64       3-tert.-butylphenyl                                                  65       4-tert.-butylphenyl                                                  66       2-tert.-butoxyphenyl                                                 67       3-tert.-butoxyphenyl                                                 68       4-tert.-butoxyphenyl                                                 69       2-phenylphenyl                                                       70       3-phenylphenyl                                                       71       4-phenylphenyl                                                       72       2-phenoxyphenyl                                                      73       3-phenoxyphenyl                                                      74       4-phenoxyphenyl                                                      75       1-naphthyl                                                           76       2-naphthyl                                                           77       2,3-Me.sub.2 -phenyl                                                 78       2,4-Me.sub.2 -phenyl                                                 79       2,5-Me.sub.2 -phenyl                                                 80       2,6-Me.sub.2 -phenyl                                                 81       3,4-Me.sub.2 -phenyl                                                 82       3,5-Me.sub.2 -phenyl                                                 83       2,4,6-Me.sub.3 -phenyl                                               84       2,3-Cl.sub.2 -phenyl                                                 85       2,4-Cl.sub.2 -phenyl                                                 86       2,5-Cl.sub.2 -phenyl                                                 87       2,6-Cl.sub.2 -phenyl                                                 88       3,4-Cl.sub.2 -phenyl                                                 89       3,5-Cl.sub.2 -phenyl                                                 90       2-pyridyl                                                            91       3-pyridyl                                                            92       4-pyridyl                                                            93       2-furyl                                                              94       3-furyl                                                              95       2-(5-NO.sub.2 -furyl)                                                96       2-thienyl                                                            97       2-(5-Cl-thienyl)                                                     98       2-(3-Cl-thienyl)                                                     99       3-(thienyl)                                                          100      2-benzofuranyl                                                       101      2-benzothienyl                                                       102      5-isoxazolyl                                                         103      3-(2-Cl-pyridyl)                                                     104      3-(6-Cl-pyridyl)                                                     105      4-(2,6-Cl.sub.2 -pyridyl)                                            106      3-(5,6-Cl.sub.2 -pyridyl)                                            107      3-(2-phenoxypyridyl)                                                 ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                         ##STR27##                                                                                            phys. data                                                                    m.p. [°C.]                                                             IR [cm.sup.-1 ]                                       No.     R.sup.18        .sup.1 H-NMR [δ scale]                          ______________________________________                                         1      OH                                                                     2      O-methyl                                                               3      O-ethyl                                                                4      O-(n-propyl)                                                           5      O-(i-propyl)                                                           6      O-(n-butyl)                                                            7      O-(i-butyl)                                                            8      O-(s-butyl)                                                            9      O-(tert.-butyl)                                                       10      O-benzyl                                                              11      O-(2-methylbenzyl)                                                    12      O-(3-methylbenzyl)                                                    13      O-(4-methylbenzyl)                                                    14      O-(2-Cl-benzyl)                                                       15      O-(3-Cl-benzyl)                                                       16      O-(4-Cl-benzyl)                                                       17      methyl                                                                18      ethyl                                                                 19      n-propyl                                                              20      i-propyl                                                              21      n-butyl                                                               22      i-butyl                                                               23      s-butyl                                                               24      tert.-butyl                                                           25      benzyl                                                                26      phenyl           89-94° C.                                     27      2-Me-phenyl      95-98° C.                                     28      3-Me-phenyl      90-92° C.                                     29      4-Me-phenyl     103-112° C.                                    30      2-F-phenyl                                                            31      3-F-phenyl                                                            32      4-F-phenyl                                                            33      2-Cl-phenyl      88-93° C.                                     34      3-Cl-phenyl      97-102° C.                                    35      4-Cl-phenyl     3.87, 4.07 (OCH.sub.3), 7.35-                                                 8.11 ppm (8H).                                        36      2-Br-phenyl                                                           37      3-Br-phenyl                                                           38      4-Br-phenyl      98-104° C.                                    39      2-I-phenyl                                                            40      3-I-phenyl                                                            41      4-I-phenyl                                                            42      2-CF.sub.3 -phenyl                                                                            2.82, 4.03 (OCH.sub.3), 7.34-                                                 8.11 ppm (8H).                                        43      3-CF.sub.3 -phenyl                                                                             88-90° C.                                     44      4-CF.sub.3 -phenyl                                                                            3.87, 4.07 (OCH.sub.3), 7.35-                                                 8.28 ppm (8H).                                        45      2-OCH.sub.3 -phenyl                                                   46      3-OCH.sub.3 -phenyl                                                   47      4-OCH.sub.3 -phenyl                                                   48      2-CN-phenyl                                                           49      3-CN-phenyl                                                           50      4-CN-phenyl                                                           51      2-NO.sub.2 -phenyl                                                    52      3-NO.sub.2 -phenyl                                                    53      4-NO.sub.2 -phenyl                                                    54      2-OCF.sub.3 -phenyl                                                   55      3-OCF.sub.3 -phenyl                                                   56      4-OCF.sub.3 -phenyl                                                   57      2-CCl.sub.3 -phenyl                                                   58      3-CCl.sub.3 -phenyl                                                   59      4-CCl.sub. 3 -phenyl                                                  60      2-NMe.sub.2 -phenyl                                                   61      3-NMe.sub.2 -phenyl                                                   62      4-NMe.sub.2 -phenyl                                                   63      2-tert.-butylphenyl                                                   64      3-tert.-butylphenyl                                                   65      4-tert.-butylphenyl                                                   66      2-tert.-butoxyphenyl                                                  67      3-tert.-butoxyphenyl                                                  68      4-tert.-butoxyphenyl                                                  69      2-phenylphenyl                                                        70      3-phenylphenyl                                                        71      4-phenylphenyl                                                        72      2-phenoxyphenyl                                                       73      3-phenoxyphenyl                                                       74      4-phenoxyphenyl                                                       75      1-naphthyl                                                            76      2-naphthyl                                                            77      2,3-Me.sub.2 -phenyl                                                  78      2,4-Me.sub.2 -phenyl                                                  79      2,5-Me.sub.2 -phenyl                                                  80      2,6-Me.sub.2 -phenyl                                                  81      3,4-Me.sub.2 -phenyl                                                  82      3,5-Me.sub.2 -phenyl                                                  83      2,4,6-Me.sub.3 -phenyl                                                84      2,3-Cl.sub.2 -phenyl                                                  85      2,4-Cl.sub.2 -phenyl                                                                          107-112° C.                                    86      2,5-Cl.sub.2 -phenyl                                                  87      2,6-Cl.sub.2 -phenyl                                                  88      3,4-Cl.sub.2 -phenyl                                                  89      3,5-Cl.sub.2 -phenyl                                                                          152-157° C.                                    90      2-pyridyl                                                             91      3-pyridyl                                                             92      4-pyridyl                                                             93      2-furyl                                                               94      3-furyl                                                               95      2-(5-NO.sub.2 -furyl)                                                 96      2-thienyl                                                             97      2-(5-Cl-thienyl)                                                      98      2-(3-Cl-thienyl)                                                      99      3-(thienyl)                                                           100     2-benzofuranyl                                                        101     2-benzothienyl                                                        102     5-isoxazolyl                                                          103     3-(2-Cl-pyridyl)                                                      104     3-(6-Cl-pyridyl)                                                      105     4-(2,6-Cl.sub.2 -pyridyl)                                             106     3-(5,6-Cl.sub.2 -pyridyl)                                             107     3-(2-phenoxypyridyl)                                                  ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                         ##STR28##                                                                                              phys. data                                                                    m.p. [°C.]                                                             IR [cm.sup.-1 ]                                     No.      R.sup.18         .sup.1 H-NMR [δ scale]                        ______________________________________                                         1       OH                                                                    2       O-methyl                                                              3       O-ethyl                                                               4       O-(n-propyl)                                                          5       O-(i-propyl)                                                          6       O-(n-butyl)                                                           7       O-(i-butyl)                                                           8       O-(s-butyl)                                                           9       O-(tert.-butyl)                                                      10       O-benzyl                                                             11       O-(2-methylbenzyl)                                                   12       O-(3-methylbenzyl)                                                   13       O-(4-methylbenzyl)                                                   14       O-(2-Cl-benzyl)                                                      15       O-(3-Cl-benzyl)                                                      16       O-(4-Cl-benzyl)                                                      17       methyl                                                               18       ethyl                                                                19       n-propyl                                                             20       i-propyl                                                             21       n-butyl                                                              22       i-butyl                                                              23       s-butyl                                                              24       tert.-butyl                                                          25       benzyl                                                               26       phenyl                                                               27       2-Me-phenyl                                                          28       3-Me-phenyl                                                          29       4-Me-phenyl                                                          30       2-F-phenyl                                                           31       3-F-phenyl                                                           32       4-F-phenyl                                                           33       2-Cl-phenyl                                                          34       3-Cl-phenyl                                                          35       4-Cl-phenyl                                                          36       2-Br-phenyl                                                          37       3-Br-phenyl                                                          38       4-Br-phenyl                                                          39       2-I-phenyl                                                           40       3-I-phenyl                                                           41       4-I-phenyl                                                           42       2-CF.sub.3 -phenyl                                                   43       3-CF.sub.3 -phenyl                                                   44       4-CF.sub.3 -phenyl                                                   45       2-OCH.sub.3 -phenyl                                                  46       3-OCH.sub.3 -phenyl                                                  47       4-OCH.sub.3 -phenyl                                                  48       2-CN-phenyl                                                          49       3-CN-phenyl                                                          50       4-CN-phenyl                                                          51       2-NO.sub.2 -phenyl                                                   52       3-NO.sub.2 -phenyl                                                   53       4-NO.sub.2 -phenyl                                                   54       2-OCF.sub.3 -phenyl                                                  55       3-OCF.sub.3 -phenyl                                                  56       4-OCF.sub.3 -phenyl                                                  57       2-CCl.sub.3 -phenyl                                                  58       3-CCl.sub.3 -phenyl                                                  59       4-CCl.sub.3 -phenyl                                                  60       2-NMe.sub.2 -phenyl                                                  61       3-NMe.sub.2 -phenyl                                                  62       4-NMe.sub.2 -phenyl                                                  63       2-tert.-butylphenyl                                                  64       3-tert.-butylphenyl                                                  65       4-tert.-butylphenyl                                                  66       2-tert.-butoxyphenyl                                                 67       3-tert.-butoxyphenyl                                                 68       4-tert.-butoxyphenyl                                                 69       2-phenylphenyl                                                       70       3-phenylphenyl                                                       71       4-phenylphenyl                                                       72       2-phenoxyphenyl                                                      73       3-phenoxyphenyl                                                      74       4-phenoxyphenyl                                                      75       1-naphthyl                                                           76       2-naphthyl                                                           77       2,3-Me.sub.2 -phenyl                                                 78       2,4-Me.sub.2 -phenyl                                                 79       2,5-Me.sub.2 -phenyl                                                 80       2,6-Me.sub.2 -phenyl                                                 81       3,4-Me.sub.2 -phenyl                                                 82       3,5-Me.sub.2 -phenyl                                                 83       2,4,6-Me.sub.3 -phenyl                                               84       2,3-Cl.sub.2 -phenyl                                                 85       2,4-Cl.sub.2 -phenyl                                                 86       2,5-Cl.sub.2 -phenyl                                                 87       2,6-Cl.sub.2 -phenyl                                                 88       3,4-Cl.sub.2 -phenyl                                                 89       3,5-Cl.sub.2 -phenyl                                                 90       2-pyridyl                                                            91       3-pyridyl                                                            92       4-pyridyl                                                            93       2-furyl                                                              94       3-furyl                                                              95       2-(5-NO.sub.2 -furyl)                                                96       2-thienyl                                                            97       2-(5-Cl-thienyl)                                                     98       2-(3-Cl-thienyl)                                                     99       3-(thienyl)                                                          100      2-benzofuranyl                                                       101      2-benzothienyl                                                       102      5-isoxazolyl                                                         103      3-(2-Cl-pyridyl)                                                     104      3-(6-Cl-pyridyl)                                                     105      4-(2,6-Cl.sub.2 -pyridyl)                                            106      3-(5,6-Cl.sub.2 -pyridyl)                                            107      3-(2-phenoxypyridyl)                                                 ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                         ##STR29##                                                                                              phys. data                                                                    m.p. [°C.]                                                             IR [cm.sup.-1 ]                                     No.      R.sup.18         .sup.1 H-NMR [δ scale]                        ______________________________________                                         1       OH                                                                    2       O-methyl                                                              3       O-ethyl                                                               4       O-(n-propyl)                                                          5       O-(i-propyl)                                                          6       O-(n-butyl)                                                           7       O-(i-butyl)                                                           8       O-(s-butyl)                                                           9       O-(tert.-butyl)                                                      10       O-benzyl                                                             11       O-(2-methylbenzyl)                                                   12       O-(3-methylbenzyl)                                                   13       O-(4-methylbenzyl)                                                   14       O-(2-Cl-benzyl)                                                      15       O-(3-Cl-benzyl)                                                      16       O-(4-Cl-benzyl)                                                      17       methyl                                                               18       ethyl                                                                19       n-propyl                                                             20       i-propyl                                                             21       n-butyl                                                              22       i-butyl                                                              23       s-butyl                                                              24       tert.-butyl                                                          25       benzyl                                                               26       phenyl                                                               27       2-Me-phenyl                                                          28       3-Me-phenyl                                                          29       4-Me-phenyl                                                          30       2-F-phenyl                                                           31       3-F-phenyl                                                           32       4-F-phenyl                                                           33       2-Cl-phenyl                                                          34       3-Cl-phenyl                                                          35       4-Cl-phenyl                                                          36       2-Br-phenyl                                                          37       3-Br-phenyl                                                          38       4-Br-phenyl                                                          39       2-I-phenyl                                                           40       3-I-phenyl                                                           41       4-I-phenyl                                                           42       2-CF.sub.3 -phenyl                                                   43       3-CF.sub.3 -phenyl                                                   44       4-CF.sub.3 -phenyl                                                   45       2-OCH.sub.3 -phenyl                                                  46       3-OCH.sub.3 -phenyl                                                  47       4-OCH.sub.3 -phenyl                                                  48       2-CN-phenyl                                                          49       3-CN-phenyl                                                          50       4-CN-phenyl                                                          51       2-NO.sub.2 -phenyl                                                   52       3-NO.sub.2 -phenyl                                                   53       4-NO.sub.2 -phenyl                                                   54       2-OCF.sub.3 -phenyl                                                  55       3-OCF.sub.3 -phenyl                                                  56       4-OCF.sub.3 -phenyl                                                  57       2-CCl.sub.3 -phenyl                                                  58       3-CCl.sub.3 -phenyl                                                  59       4-CCl.sub.3 -phenyl                                                  60       2-NMe.sub.2 -phenyl                                                  61       3-NMe.sub.2 -phenyl                                                  62       4-NMe.sub.2 -phenyl                                                  63       2-tert.-butylphenyl                                                  64       3-tert.-butylphenyl                                                  65       4-tert.-butylphenyl                                                  66       2-tert.-butoxyphenyl                                                 67       3-tert.-butoxyphenyl                                                 68       4-tert.-butoxyphenyl                                                 69       2-phenylphenyl                                                       70       3-phenylphenyl                                                       71       4-phenylphenyl                                                       72       2-phenoxyphenyl                                                      73       3-phenoxyphenyl                                                      74       4-phenoxyphenyl                                                      75       1-naphthyl                                                           76       2-naphthyl                                                           77       2,3-Me.sub.2 -phenyl                                                 78       2,4-Me.sub.2 -phenyl                                                 79       2,5-Me.sub.2 -phenyl                                                 80       2,6-Me.sub.2 -phenyl                                                 81       3,4-Me.sub.2 -phenyl                                                 82       3,5-Me.sub.2 -phenyl                                                 83       2,4,6-Me.sub.3 -phenyl                                               84       2,3-Cl.sub.2 -phenyl                                                 85       2,4-Cl.sub.2 -phenyl                                                 86       2,5-Cl.sub.2 -phenyl                                                 87       2,6-Cl.sub.2 -phenyl                                                 88       3,4-Cl.sub.2 -phenyl                                                 89       3,5-Cl.sub.2 -phenyl                                                 90       2-pyridyl                                                            91       3-pyridyl                                                            92       4-pyridyl                                                            93       2-furyl                                                              94       3-furyl                                                              95       2-(5-NO.sub.2 -furyl)                                                96       2-thienyl                                                            97       2-(5-Cl-thienyl)                                                     98       2-(3-Cl-thienyl)                                                     99       3-(thienyl)                                                          100      2-benzofuranyl                                                       101      2-benzothienyl                                                       102      5-isoxazolyl                                                         103      3-(2-Cl-pyridyl)                                                     104      3-(6-Cl-pyridyl)                                                     105      4-(2,6-Cl.sub.2 -pyridyl)                                            106      3-(5,6-Cl.sub.2 -pyridyl)                                            107      3-(2-phenoxypyridyl)                                                 ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                         ##STR30##                                                                                           phys. data                                                                    m.p. [°C.]                                                             IR [cm.sup.-1 ]                                        No.    R.sup.20        .sup.1 H-NMR [δ scale]                           ______________________________________                                         1     methyl                                                                  2     ethyl                                                                   3     n-propyl                                                                4     i-propyl                                                                5     n-butyl                                                                 6     i-butyl                                                                 7     s-butyl                                                                 8     tert.-butyl                                                             9     benzyl                                                                 10     phenyl          3.81; 4.04; 4.12 (CH.sub.3);                                                  7.28-7.88 ppm (9H)                                     11     2-Me-phenyl                                                            12     3-Me-phenyl     2.42; 3.81, 4.05; 4.12 (CH.sub.3);                                            7.17-7.71 ppm (8H).                                    13     4-Me-phenyl     2.38; 3.82; 4.05; 4.11 (CH.sub.3);                                            7.18-7.75 ppm (8H).                                    14     2-F-phenyl                                                             15     3-F-phenyl                                                             16     4-F-phenyl                                                             17     2-Cl-phenyl     3.76; 4.00; 4.12 (CH.sub.3);                                                  7.28-7.61 ppm (8H).                                    18     3-Cl-phenyl                                                            19     4-Cl-phenyl                                                            20     2-Br-phenyl                                                            21     3-Br-phenyl                                                            22     4-Br-phenyl                                                            23     2-I-phenyl                                                             24     3-I-phenyl                                                             25     4-I-phenyl                                                             26     2-CF.sub.3 -phenyl                                                     27     3-CF.sub.3 -phenyl                                                                            3.81; 4.05; 4.15 (CH.sub.3);                                                  7.28-8.11 ppm (8H).                                    28     4-CF.sub.3 -phenyl                                                                            3.82; 4.05; 4.15 (CH.sub.3);                                                  7.30-7.98 ppm (8H).                                    29     2-OCH.sub.3 -phenyl                                                    30     3-OCH.sub.3 -phenyl                                                    31     4-OCH.sub.3 -phenyl                                                    32     2-CN-pheny                                                             33     3-CN-phenyl                                                            34     4-CN-phenyl                                                            35     2-NO.sub.2 -phenyl                                                     36     3-NO.sub.2 -phenyl                                                     37     4-NO.sub.2 -phenyl                                                     38     2-OCF.sub.3 -phenyl                                                    39     3-OCF.sub.3 -phenyl                                                    40     4-OCF.sub.3 -phenyl                                                    41     2-CCl.sub.3 - phenyl                                                   42     3-CCl.sub.3 - phenyl                                                   43     4-CCl.sub.3 - phenyl                                                   44     2-NMe.sub.2 - phenyl                                                   45     3-NMe.sub.2 - phenyl                                                   46     4-NMe.sub.2 - phenyl                                                   47     2-tert.-butylphenyl                                                    48     3-tert.-butylphenyl                                                    49     4-tert.-butylphenyl                                                    50     2-tert.-butoxyphenyl                                                   51     3-tert.-butoxyphenyl                                                   52     4-tert.-butoxyphenyl                                                   53     2-phenylphenyl                                                         54     3-phenylphenyl                                                         55     4-phenylphenyl                                                         56     2-phenoxyphenyl                                                        57     3-phenoxyphenyl                                                        58     4-phenoxyphenyl                                                        59     1-naphthyl                                                             60     2-naphthyl                                                             61     2,3-Me.sub.2 -phenyl                                                   62     2,4-Me.sub.2 -phenyl                                                   63     2,5-Me.sub.2 -phenyl                                                   64     2,6-Me.sub.2 -phenyl                                                   65     3,4-Me.sub.2 -phenyl                                                   66     3,5-Me.sub.2 -phenyl                                                   67     2,4,6-Me.sub.3 -phenyl                                                 68     2,3-Cl.sub.2 -phenyl                                                   69     2,4-Cl.sub.2 -phenyl                                                   70     2,5-Cl.sub.2 -phenyl                                                   71     2,6-Cl.sub.2 -phenyl                                                   72     3,4-Cl.sub.2 -phenyl                                                   73     3,5-Cl.sub.2 -phenyl                                                   74     2-pyridyl                                                              75     3-pyridyl                                                              76     4-pyridyl                                                              77     2-furyl                                                                78     3-furyl                                                                79     2-(5-NO.sub.2 -furyl)                                                  80     2-thienyl                                                              81     2-(5-Cl-thienyl)                                                       82     2-(3-Cl-thienyl)                                                       83     3-(thienyl)                                                            84     2-benzofuranyl                                                         85     2-benzothienyl                                                         86     5-isoxazolyl                                                           87     3-(2-Cl-pyridyl)                                                       88     3-(6-Cl-pyridyl)                                                       89     4-(2,6-Cl.sub.2 -pyridyl)                                              90     3-(5,6-Cl.sub.2 -pyridyl)                                              91     3-(2-phenoxypyridyl)                                                   ______________________________________                                    

                  TABLE 10                                                        ______________________________________                                         ##STR31##                                                                                           phys. data                                                                    m.p. [°C.]                                                             IR [cm.sup.-1 ]                                        No.    R.sup.20        .sup.1 H-NMR [δ scale]                           ______________________________________                                         1     methyl                                                                  2     ethyl                                                                   3     n-propyl                                                                4     i-propyl                                                                5     n-butyl                                                                 6     i-butyl                                                                 7     s-butyl                                                                 8     tert.-butyl                                                             9     benzyl                                                                 10     phenyl          2.85 (d, 3H); 3.94; 4.10                                                      (CH.sub.3); 6.79 (NH), 7.28-                                                  7.84 ppm (9H)                                          11     2-Me-phenyl                                                            12     3-Me-phenyl                                                            13     4-Me-phenyl                                                            14     2-F-phenyl                                                             15     3-F-phenyl                                                             16     4-F-phenyl                                                             17     2-Cl-phenyl                                                            18     3-Cl-phenyl                                                            19     4-Cl-phenyl                                                            20     2-Br-phenyl                                                            21     3-Br-phenyl                                                            22     4-Br-phenyl                                                            23     2-I-phenyl                                                             24     3-I-phenyl                                                             25     4-I-phenyl                                                             26     2-CF.sub.3 -phenyl                                                     27     3-CF.sub.3 -phenyl                                                     28     4-CF.sub.3 -phenyl                                                     29     2-OCH.sub.3 -phenyl                                                    30     3-OCH.sub.3 -phenyl                                                    31     4-OCH.sub.3 -phenyl                                                    32     2-CN-phenyl                                                            33     3-CN-phenyl                                                            34     4-CN-phenyl                                                            35     2-NO.sub.2 -phenyl                                                     36     3-NO.sub.2 -phenyl                                                     37     4-NO.sub.2 -phenyl                                                     38     2-OCF.sub.3 -phenyl                                                    39     3-OCF.sub.3 -phenyl                                                    40     4-OCF.sub.3 -phenyl                                                    41     2-CCl.sub.3 - phenyl                                                   42     3-CCl.sub.3 - phenyl                                                   43     4-CCl.sub.3 - phenyl                                                   44     2-NMe.sub.2 - phenyl                                                   45     3-NMe.sub.2 - phenyl                                                   46     4-NMe.sub.2 - phenyl                                                   47     2-tert.-butylphenyl                                                    48     3-tert.-butylphenyl                                                    49     4-tert.-butylphenyl                                                    50     2-tert.-butoxyphenyl                                                   51     3-tert.-butoxyphenyl                                                   52     4-tert.-butoxyphenyl                                                   53     2-phenylphenyl                                                         54     3-phenylphenyl                                                         55     4-phenylphenyl                                                         56     2-phenoxyphenyl                                                        57     3-phenoxyphenyl                                                        58     4-phenoxyphenyl                                                        59     1-naphthyl                                                             60     2-naphthyl                                                             61     2,3-Me.sub.2 -phenyl                                                   62     2,4-Me.sub.2 -phenyl                                                   63     2,5-Me.sub.2 -phenyl                                                   64     2,6-Me.sub.2 -phenyl                                                   65     3,4-Me.sub.2 -phenyl                                                   66     3,5-Me.sub.2 -phenyl                                                   67     2,4,6-Me.sub.3 -phenyl                                                 68     2,3-Cl.sub.2 -phenyl                                                   69     2,4-Cl.sub.2 -phenyl                                                   70     2,5-Cl.sub.2 -phenyl                                                   71     2,6-Cl.sub.2 -phenyl                                                   72     3,4-Cl.sub.2 -phenyl                                                   73     3,5-Cl.sub.2 -phenyl                                                   74     2-pyridyl                                                              75     3-pyridyl                                                              76     4-pyridyl                                                              77     2-furyl                                                                78     3-furyl                                                                79     2-(5-NO.sub.2 -furyl)                                                  80     2-thienyl                                                              81     2-(5-Cl-thienyl)                                                       82     2-(3-Cl-thienyl)                                                       83     3-(thienyl)                                                            84     2-benzofuranyl                                                         85     2-benzothienyl                                                         86     5-isoxazolyl                                                           87     3-(2-Cl-pyridyl)                                                       88     3-(6-Cl-pyridyl)                                                       89     4-(2,6-Cl.sub.2 -pyridyl)                                              90     3-(5,6-Cl.sub.2 -pyridyl)                                              91     3-(2-phenoxypyridyl)                                                   ______________________________________                                    

The novel compounds are suitable as fungicides.

The fungicidal compounds according to the invention, or agentscontaining them, may be applied for instance in the form of directlysprayable solutions, powders, suspensions (including high-percentageaqueous, oily or other suspensions), dispersions, emulsions, oildispersions, pastes, dusts, broadcasting agents, or granules byspraying, atomizing, dusting, broadcasting or watering. The forms ofapplication depend entirely on the purpose for which the agents arebeing used, but they must ensure as fine a distribution of the activeingredients according to the invention as possible.

Normally, the plants are sprayed or dusted with the active ingredientsor the seeds of the plants are treated with the active ingredients.

The formulations are produced in known manner, for example by extendingthe active ingredient with solvents and/or carriers, with or without theuse of emulsifiers and dispersants; if water is used as solvent, it isalso possible to employ other organic solvents as auxiliary solvents.Suitable auxiliaries for this purpose are solvents such as aromatics(e.g., xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins(e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones(e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide),and water; carriers such as ground natural minerals (e.g., kaolins,aluminas, talc and chalk) and ground synthetic minerals (e.g., highlydisperse silica and silicates); emulsifiers such as nonionic and anionicemulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkylsulfonates and aryl sulfonates); and dispersants such as lignin-sulfitewaste liquors and methylcellulose.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid,phenolsulfonic acid, naphthalenesulfonic acid anddibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, andsalts of sulfated hexadecanols, heptadecanols, and octadecanols, saltsof fatty alcohol glycol ethers, condensation products of sulfonatednaphthalene and naphthalene derivatives with formaldehyde, condensationproducts of naphthalene or naphthalenesulfonic acids with phenol andformaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcoholethylene oxide condensates, ethoxylated castor oil, polyoxyethylenealkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycolether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silicic acids, silica gels,silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesiumsulfate, magnesium oxide, ground plastics, fertilizers such as ammoniumsulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetableproducts such as grain meals, bark meal, wood meal, and nutshell meal,cellulosic powders, etc.

Examples of such formulations are given below.

I. A solution of 90 parts by weight of compound no. 1 from Table 2 and10 parts by weight of N-methyl-α-pyrrolidone, which is suitable forapplication in the form of very fine drops.

II. A mixture of 20 parts by weight of compound no. 24 from Table 2, 80parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 moleof castor oil. By finely dispersing the mixture in water, a dispersionis obtained.

III. An aqueous dispersion of 20 parts by weight of compound no. 25 fromTable 2, 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 40 moles of ethyleneoxide and 1 mole of castor oil.

IV. An aqueous dispersion of 20 parts by weight of compound no. 26 fromTable 2, 25 parts by weight of cyclohexanol, 65 parts by weight of amineral oil fraction having a boiling point between 210° and 280° C.,and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1mole of castor oil.

V. A hammer-milled mixture of 80 parts by weight of compound no. 31 fromTable 2, 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodiumsalt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and7 parts by weight of powdered silica gel. By finely dispersing themixture in water, a spray liquor is obtained.

VI. An intimate mixture of 3 parts by weight of compound no. 33 fromTable 2 and 97 parts by weight of particulate kaolin. The dust contains3 wt % of the active ingredient.

VII. An intimate mixture of 30 parts by weight of compound no. 34 fromTable 2, 92 parts by weight of powdered silica gel and 8 parts by weightof paraffin oil sprayed onto the surface of this silica gel. Thisformulation of the active ingredient exhibits good adherence.

VIII. A stable aqueous dispersion of 40 parts by weight of compound no.35 from Table 2, 10 parts of the sodium salt of a phenolsulfonicacid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts ofwater, which dispersion can be further diluted.

IX. A stable oily dispersion of 20 parts by weight of compound no. 42from Table 2, 2 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcoholpolyglycol ether, 2 parts by weight of the sodium salt of aphenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weightof a paraffinic mineral oil.

The novel compounds are extremely effective on a broad spectrum ofphytopathogenic fungi, in particular those from the class consisting ofthe Ascomycetes and Basidiomycetes. Some of them have a remarkably highsystemic mobility and action after application to the soil andparticularly to foliage.

The fungicidal compounds are of particular interest for controlling alarge number of fungi in various crops or their seeds, especially wheat,rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee,sugar cane, fruit and ornamentals in horticulture and viticulture, andin vegetables such as cucumbers, beans and cucurbits.

The compounds are applied by treating the seeds, plants, materials orsoil to be protected against fungus attack with a fungicidally effectiveamount of the active ingredients.

The compounds may be applied before or after infection of the materials,plants or seeds by the fungi.

The compounds I are particularly useful for controlling the followingplant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia solani in cotton,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

H elminthosporium species in cereals,

Septoria nodorum in wheat,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in fruit and vegetables.

The novel compounds may also be used for protecting materials (timber),for example against Paecilomyces variotii.

The fungicidal agents generally contain from 0.1 to 95, and preferablyfrom 0.5 to 90, wt % of active ingredient.

The application rates depend on the type of effect desired, but aregenerally from 0.02 to 3 kg of active ingredient per hectare.

When the active ingredients are used for treating seed, applicationrates of from 0.001 to 50, and preferably from 0.01 to 10, g per kg ofseed are generally required.

When the agents according to the invention are used as fungicides, theymay be employed together with other active ingredients, e.g.,herbicides, insecticides, growth regulators, other fungicides andfertilizers.

When admixed with other fungicides, the spectrum of fungicidal action isin many instances increased.

Use examples

In the active ingredients used for comparison purposes, U, V and W=H,A=CH₃ ON═, B=CH₃ O and R=phenyl (compound 1), R=2-chlorophenyl (compoundB) , and R=4-CF₃ -phenyl (compound C). All of these compounds are knownfrom EP 253 213.

Use Example 1

Action on cucumber mildew

Young cucumber plants of the "Chinesische Schlange" variety were sprayedto runoff at the two-leaf stage with an aqueous spray liquor. The nextday these plants were sprayed with an aqueous conidial suspension ofcucumber mildew (Erysiphe cichoracearum and Sphaerotheca fuliginea), andkept in the greenhouse at 20° to 22° C. and a relative humidity of 70 to80%. The extent of fungus spread was determined 21 days afterapplication of the active ingredients.

The results show that the active ingredients from Table 2, no. 33(2,33), 2,43; 2,148 and 2,166 have, when applied as a spray liquorcontaining 63 ppm of active ingredient, a better fungicidal action (10%leaf attack) than prior art comparative active ingredients A, B and C(45% leaf attack).

Use Example 2

Action on Botrytis cinerea in paprika pods (fruit test)

Slices of green paprika pods were sprayed to runoff with aqueousformulations containing 80% of active ingredient and 20% of emulsifier.Two hours after the sprayed-on layer had dried, the slices wereinoculated with a spore suspension of Botrytis cinerea containing1.7×10⁶ spores per ml of a 2% biomalt solution. The inoculated sliceswere then incubated in moist chambers for 4 days at 18° C. The extent ofBotrytis spread on the slices was then assessed visually.

The results show that active ingredients 2,25; 2,35; 2,166 and 2,179,when applied as spray liquors containing 500 ppm of active ingredient,have a better fungicidal action (10% attack) than prior art comparativeactive ingredient A (30% attack).

Use Example 3

Action on Plasmopara viticola

Leaves of potted vines of the Muller-Thurgau variety were sprayed withaqueous suspensions containing (dry basis) 80% of active ingredient and20% of emulsifier. To assess the duration of action, the plants were setup, after the sprayed-on layer had dried, for 8 days in the greenhouse.Then the leaves were infected with a zoospore suspension of Plasmoparaviticola. The plants were first placed for 48 hours in a watervapor-saturated chamber at 24° C. and then in a greenhouse for 5 days atfrom 20° to 30° C. To accelerate and intensify the sporangiophoredischarge, the plants were then again placed in the moist chamber for 16hours. The extent of fungus attack was then assessed on the undersidesof the leaves.

The results show that active ingredients 1,195; 2,25; 2,35; 2,43; 2,86;2,88; 2,92; 2,94; 2,95 and 2,148, when applied as spray liquorscontaining 16 ppm of active ingredient, have a better fungicidal action(5% leaf attack) than prior art comparative active ingredient C (35%leaf attack).

We claim:
 1. An acetylene derivative of the formula I ##STR32## where U,V and W are identical or different and are each hydrogen, halogen,nitro, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,A is C₁ -C₄ -alkoximino, Bis OH or C₁ -C₄ -alkoxy and R is hydrogen, halogen, cyano, CF₃,straight-chain or branched C₁ -C₁₀ -alkyl, C₃ -C₆ -cycloalkyl,unsubstituted or substituted aryl, halo-C₁ -C₄ -alkyl, C₂ -C₆ -alkenyl,C₂ -C₄ -alkynyl, unsubstituted or substituted aryl-C₁ -C₄ -alkyl,unsubstituted or substituted aryl-C₂ -C₄ -alkenyl, unsubstituted orsubstituted arylethynyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, unsubstituted orsubstituted aryloxy-C₁ -C₄ -alkyl, unsubstituted or substitutedarylamino-C₁ -C₄ -alkyl, unsubstituted or substituted arylthiomethyl,C(O)R¹, C(O)NR² R³, C(S)NR⁴ R⁵, C(O)SR⁶, C(S)OR⁷, C(S)SR⁸, CH(OH)R⁹,CH(OR¹⁰)R¹¹, C(OR)R¹⁸ or C(═N--OR¹⁹)R²⁰ and R¹ --R¹⁷, R¹⁹ and R²⁰ areidentical or different and are each hydrogen, C₁ -C₄ -alkyl,unsubstituted or substituted aryl or unsubstituted or substitutedarylalkyl, R¹⁸ is OH, C₁ -C₄ -alkoxy or unsubstituted or substitutedaryl-C₁ -C₄ -alkoxy, the term "unsubstituted or substituted" denoting,in addition to hydrogen, halogen, cyano, nitro, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkoximino-C₁-C₄ -alkyl, aryl, aryloxy, benzyl, benzyloxy, C₃ -C₆ -cycloalkyl, C₁ -C₄-dialkylamino, CO₂ Me, CO₂ Et, formyl or acyl and Me is methyl and Et isethyl, with the exception of the following individual compounds of theformula I where A=CHOCH₃, B=OCH₃ and R=phenyl A=CHSCH₃, B=OCH₃ andR=phenyl A=CHCH₃, B=OCH₃, and R=phenyl, 2-fluorophenyl, 2-chlorophenyl,2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl,4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl, A=NOCH₃,B=OCH₃ and R=phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl,2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl,4-trifluoromethylphenyl or 4-methylphenyl, A=NOCH₃, B=NHCH₃, R=CH₃,phenyl, A=CHOCH₃, B=NHCH₃, R=CH₃, phenyl and A=CHSCH₃, B=NHCH₃,R=phenyl.
 2. An acetylene derivative of the formula III ##STR33## whereR is a defined in claim
 1. 3. An acetylene derivative of the formula VII##STR34## where A and B are as defined in claim
 1. 4. A fungicidecontaining an inert carrier and a fungicidally effective amount of anacetylene derivative of the formula I ##STR35## where U, V and W areidentical or different and are each hydrogen, halogen, nitro, cyano, C₁-C₄ -alkyl or C₁ -C₄ -alkoxy,A is C₁ -C₄ -alkoximino, B is OH or C₁ -C₄-alkoxy and R is hydrogen, halogen, cyano, CF₃, straight-chain orbranched C₁ -C₁₀ -alkyl, C₃ --C₆ -cycloalkyl, unsubstituted orsubstituted aryl, halo-C₁ -C₄ -alkyl, C₂ -C₆ -alkenyl, C₂ -C₄ -alkynyl,unsubstituted or substituted aryl-C₁ -C₄ -alkyl, unsubstituted orsubstituted aryl-C₂ -C₄ -alkenyl, unsubstituted or substitutedarylethynyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, unsubstituted or substitutedaryloxy-C₁ -C₄ -alkyl, unsubstituted or substituted arylamino-C₁ -C₄-alkyl, unsubstituted or substituted arylthiomethyl, C(O)R¹, C(O)NR² R³,C(S)NR⁴ R⁵, C(O)SR⁶, C(S)OR⁷, C(S)SR⁸, CH(OH)R⁹, CH(OR¹⁰)R¹¹, C(OR)R¹⁸or C(═N--OR¹⁹)R²⁰ and R¹ -R¹⁷, R¹⁹ and R²⁰ are identical or differentand are each hydrogen, C₁ -C₄ -alkyl, unsubstituted or substituted arylor unsubstituted or substituted arylalkyl, R¹⁸ is OH, C₁ -C₄ -alkoxy orunsubstituted or substituted aryl-C₁ -C₄ -alkoxy, the term"unsubstituted or substituted" denoting, in addition to hydrogen,halogen, cyano, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl,C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkoximino-C₁ -C₄ -alkyl, aryl, aryloxy,benzyl, benzyloxy, C₃ -C₆ -cycloalkyl, C₁ -C₄ -dialkylamino, CO₂ Me, CO₂Et, formyl or acyl and Me is methyl and Et is ethyl, with the exceptionof the following individual compounds of the formula I where A=CHOCH₃,B=OCH₃ and R=phenyl A=CHSCH₃, B=OCH₃ and R=phenyl A=CHCH₃, B=OCH₃, andR=phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl,2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl,4-trifluoromethylphenyl or 4-methylphenyl, A=NOCH₃, B=OCH₃ and R=phenyl,2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl,2-nitrophenyl, 2-methylphenyl, 4-bromophenyl, 4-trifluoromethylphenyl or4-methylphenyl, A=NOCH₃, B=NHCH₃, R=CH₃, phenyl, A=CHOCH₃, B=NHCH₃,R=CH₃, phenyl and A=CHSCH₃, B=NHCH₃, R=phenyl.
 5. A method of combattingfungi, wherein the fungi, or the materials, plants or seeds to beprotected against fungus attack, or the soil are treated with afungicidally effective amount of a compound of the formula ##STR36##where U, V and W are identical or different and are each hydrogen,halogen, nitro, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,A is C₁ -C₄-alkoximino, B is OH or C₁ -C₄ -alkoxy and R is hydrogen, halogen,cyano, CF₃, straight-chain or branched C₁ -C₁₀ -alkyl, C₃ -C₆-cycloalkyl, unsubstituted or substituted aryl, halo-C₁ -C₄ -alkyl, C₂-C₆ -alkenyl, C₂ -C₄ -alkynyl, unsubstituted or substituted aryl-C₁ -C₄-alkyl, unsubstituted or substituted aryl-C₂ -C₄ -alkenyl, unsubstitutedor substituted arylethynyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, unsubstitutedor substituted aryloxy-C₁ -C₄ -alkyl, unsubstituted or substitutedarylamino-C₁ -C₄ -alkyl, unsubstituted or substituted arylthiomethyl,C(O)R¹, C(O)NR¹ R³, C(S)NR⁴ R⁵, C(O)SR⁶, C(S)OR⁷, C(S)SR⁸, CH(OH)R⁹,CH(OR¹⁰)R¹¹, C(OR)R¹⁸ or C(═N--OR¹⁹)R²⁰ and R¹ -R¹⁷, R¹⁹ and R²⁰ areidentical or different and are each hydrogen, C¹ -C₄ -alkyl,unsubstituted or substituted aryl or unsubstituted or substitutedarylalkyl, R¹⁸ is OH, C₁ -C₄ -alkoxy or unsubstituted or substitutedaryl-C₁ -C₄ -alkoxy, the term "unsubstituted or substituted" denoting,in addition to hydrogen, halogen, cyano, nitro, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkoximino-C₁-C₄ -alkyl, aryl, aryloxy, benzyl, benzyloxy, C₃ -C₆ -cycloalkyl, C₁ -C₄-dialkylamino, CO₂ Me, CO₂ Et, formyl or acyl and Me is methyl and Et isethyl, with the exception of the following individual compounds of theformula I where A=CHOCH₃, B=OCH₃ and R=phenyl A=CHSCH₃, B=OCH₃ andR=phenyl A=CHCH₃, B=OCH₃, and R=phenyl, 2-fluorophenyl, 2-chlorophenyl,2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl,4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl, A=NOCH₃,B=OCH₃ and R=phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl,2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl,4-trifluoromethylphenyl or 4-methylphenyl, A=NOCH₃, B=NHCH₃, R=CH₃,phenyl, A=CHOCH₃, B=NHCH₃, R=CH₃, phenyl and A=CHSCH₃, B=NHCH₃,R=phenyl.
 6. The acetylene derivative of claim 1, wherein R is hydrogen,halogen, cyano, CF₃, straight-chain or branched C₁ -C₁₀ -alkyl, C₃ -C₆-cycloalkyl, halo-C₁ -C₄ -alkyl, C₂ -C₆ -alkenyl, C₂ -C₄ -alkynyl,unsubstituted or substituted aryl-C₁ -C₄ -alkyl, unsubstituted orsubstituted aryl-C₂ -C₄ -alkenyl, unsubstituted or substitutedaryl-ethynyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, unsubstituted or substitutedaryloxy-C₁ -C₄ -alkyl, unsubstituted or substituted arylamino-C₁ -C₄-alkyl, unsubstituted or substituted arylthiomethyl C(O)R¹, C(O)NR² R³,C(S)NR⁴ R⁵, C(O)SR⁶, C(S)OR⁷, C(S)SR⁸, CH(OH)R⁹, CH(OR¹⁰)R¹¹, C(O)R¹⁶ orC(═N--OR¹⁹)R²⁰.
 7. The acetylene derivative of claim 2, wherein R isphenyl substituted with halogen, cyano, nitro, C₁ -C₄ alkoxy, C₁ -C₄-haloalkyl, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkoxyimino-C₁ -C₄ -alkyl, aryl,aryloxy, benzyl, benzyloxy, C₃ -C₆ -cycloalkyl, C₁ -C₄ -dialkylamino,CO₂ Me, CO₂ Et, formyl or acyl.
 8. The acetylene derivative of claim 7,wherein R is selected from the group consisting of 2,3-Me₂ -phenyl,2,4-Me₂ -phenyl, 2,5-Me₂ -phenyl, 2,6-Me₂ -phenyl, 3,4-Me₂ -phenyl,3,5-Me₂ -phenyl and 2,4,6-Me₃ -phenyl.
 9. The acetylene derivative ofclaim 2, wherein R is selected from the group consisting of 2-CN-phenyl,3-CN-phenyl, 4-CN-phenyl, 2-(CH₂ CN)-phenyl, 3-(CH₂ CN)-phenyl and4-(CH₂ CN)-phenyl.
 10. The acetylene derivative of claim 9, wherein R is3-(CH₂ CN)-phenyl.